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Electrochemical stability on 1-ethyl-3-methylimidazolium bis

(trifluoromethyl sulfonyl) imide ionic liquid for dye sensitized
solar cell application

Muhammad-Alif Lohmoh, Mohd Dzul Hakim Wirzal, Nur

Syakinah Abd Halim, Muhammad Syaamil Saad, Choi Yee Foong

PII: S0167-7322(20)32844-0
DOI: https://doi.org/10.1016/j.molliq.2020.113594
Reference: MOLLIQ 113594

To appear in: Journal of Molecular Liquids

Received date: 4 May 2020

Revised date: 29 May 2020
Accepted date: 12 June 2020

Please cite this article as: M.-A. Lohmoh, M.D.H. Wirzal, N.S.A. Halim, et al.,
Electrochemical stability on 1-ethyl-3-methylimidazolium bis (trifluoromethyl sulfonyl)
imide ionic liquid for dye sensitized solar cell application, Journal of Molecular Liquids
(2020), https://doi.org/10.1016/j.molliq.2020.113594

This is a PDF file of an article that has undergone enhancements after acceptance, such
as the addition of a cover page and metadata, and formatting for readability, but it is
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version to give early visibility of the article. Please note that, during the production
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that apply to the journal pertain.

© 2020 Published by Elsevier.

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Electrochemical Stability on 1-Ethyl-3-Methylimidazolium bis (trifluoromethyl

sulfonyl) Imide Ionic Liquid for Dye Sensitized Solar Cell Application
Muhammad-Alif Lohmoh a, Mohd Dzul Hakim Wirzal a,b*, Nur Syakinah Abd Halim a,
Muhammad Syaamil Saad a and Choi Yee Foong a

a
Chemical Engineering Department, Universiti Teknologi PETRONAS, 32610 Bandar Seri Iskandar,
Perak, Malaysia

b
Center of Research in Ionic Liquids (CORIL), Universiti Teknologi PETRONAS, 32610 Bandar

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Seri Iskandar, Perak, Malaysia

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ABSTRACT
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The usage of ionic liquids has recently became a promosing alternative for
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replacement of conventional volatile organic-based electrolyte for Dye Sensitized
Solar Cells (DSSCs) due to its electrochemical stability, high conductivity and low
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vapor pressure. However, degradation of ionic liquid concentration is one of the major
concerns which affect the efficiency of DSSCs. By using electro-oxidation method,
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this research aimed to evaluate the degradation of 1-Ethyl-3-Methylimidazolium bis

(trifluoromethyl sulfonyl) imide [EMIM][N(Tf)2] ionic liquid by analyzing the change
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of concentration with respect to high voltage differences (i.e., 1V, 2V, 4V, 6V, 8V
and 10V). FT-IR result shows that there is slight degradation in the concentration
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amount of [EMIM][N(Tf)2] ionic liquid which is almost negligible and there is no

change in spectrum as well as functional group when compared with standard curve
of [EMIM][N(Tf)2] ionic liquid from 1V to 10V. Apart from that, the degradation
percentage of each voltage at 60 min are 8.48%, 7.90%, 3.82%, 6.08%, 3.51% and
2.86 %, respectively. The highest Iron (Fe) amount was 224.45 ppm at the condition
of 6V at 5 min. It is proven that [EMIM][N(Tf)2] has high capability to be used as an
electrolyte as it has high electrochemical stability in the voltage range from 1V to
10V.

Keywords: [EMIM][N(Tf)2] ionic liquid; electrochemical stability; electro-oxidation

method
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*Correspondence authors
Email addresses: mdzulhakim.wirzal@utp.edu.my

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1.0 Introduction

For the past years, ionic liquids (ILs) have been used extensively in numerous
kinds of fields especially for catalysis, synthesis, CO2 capture and separation
technology. A review by Siedlecka et al. (2011) mentioned that the high potential
usage of ILs in various application was due to its great properties i.e., negligible vapor
pressure and non-flammability under ambient conditions, high thermal conductivity,
wide electrochemical window and high polarity [1]. Dye-sensitized solar cells
(DSSCs) is one of the commonly and interesting application of ILs in
commercialization purpose. Over the past few decades, DSSCs has been considered

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as one of the reliable renewable energy sources due to its remarkable properties such

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as ease fabrication processes in ambient conditions, low cost and reasonable cell
efficiency for commercialization [2–5]. Generally, DSSCs is build up by three major
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components; semiconductor, dye and electrolyte. The properties of electrolyte is very
crucial in mantaining the long-term stability of DSSCs [5]. Electrolyte in DSSCs
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helps in regenerating the dye after it injects electrons into the conduction band of the
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semiconductor apart from acting as a charge transport medium to transfer positive

charges toward the counter electrodes.
Furthermore, organic solvent based electrolytes and room temperature ionic
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liquid electrolytes are the commonly used electrolyte for DSSCs application.
Nevertheless, organic solvent based electrolyte has high volatility which eventually
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caused evaporation under thermal stress and worsen the cell condition over prolonged
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use [6]. Hence, IL is more favourable since it has good chemical and thermal stability,
high ionic conductivity, tuneable viscosity and also low volatility [7–10]. Basically,
ILs used in DSSCs can be divided into two groups: imidazolium and nonimidazolium
cations. The research of ionic liquid-based electrolytes in DSSCs is usually focused
more on imidazolium-base [9]. Moreover, the conversion efficiencies of DSSC with
imidazolium-based IL is more preferrable as it gives higher conversion than non-
imidazolium based IL. Apart from being commonly used electrolyte in DSSCs [11–
14], [EMIM][N(Tf)2] IL is also one of the widely used imidazolium cation due to its
alkyl chain length, cation and anion properties.
Apart from that, for electrochemical stability properties, the high voltage
differences of IL with respect to the stability characteristics of IL is one of the most
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important factor in electrochemical application such as fuel cell batteries and dye
solar cell. High electrochemical stability is essentially important in order to reach high
energy and power density of electrochemical devices. A study by Kroon et.al. (2006)
mentioned that ILs decomposed when voltage differences is larger than their
electrochemical window (normally in between range of 4-6 V) [15]. On the other
hand, impurities such as residual halides and water were able to be affected by the
electrochemical stability of ILs [1,16]. The water content in ILs causes narrowing of
electrochemical potential window at both the cathodic and anodic limits. This
correlated with the study by Li et al. (2016) which found that the influence of the
water content on the electrochemical stability is reduced [17].

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Meanwhile, a study by Borland et.al. (2007) mentioned on the different kinds

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of electrochemical methods to determine electrochemical windows [18]. They were
voltammetry and potentiometry methods. Potentiometry methods generally are
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measurements that do not involve current, while for voltammetry methods, they
involve current flow at an electrode under potential control depending upon the details
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of the experimental design. Potentiometry (or electro-oxidation) method was selected
due to its less complexity and easy to setup. Apart from that, it has been reported that
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electro-oxidation is highly capable in degrading different types of organic pollutants,

pharmaceuticals and pesticides [19,20]. Chiang et.al. (1995) stated that there are two
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different mechanisms involved in this method: (1) direct anodic oxidation, where the
electrolytes are destroyed at the anode surface and (2) indirect oxidation where the
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mediators are electrochemically produced to achieve the oxidation [21]. Drogui et.al.
(2007) illustrated the chemical reaction of direction oxidation [22] as shown in
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Equation 1 and Equation 2 while, Li et.al. (2010) and Scialdone et.al. (2009)
explained indirect oxidation by using chlorine/hypochlorite as an oxidizing agent
which was illustrated from Equation 3 to Equation 9 [23,24].

Electrochemical ( ) (1)
conversion
Electrochemical ( ) (2)
combustion
Anodic reaction (3)
Anodic reaction (4)
Anodic reaction (5)
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Bulk reaction (6)

Bulk reaction (7)
Cathodic reaction (8)
Cathodic reaction ) (9)

In the literature as aforementioned, a vast majority of experiments focus more

on the effectiveness of generated electricity by introducing the ILs as an electrolyte,
meanwhile to our best knowledge, only few studies have been conducted for the
electrochemical stability of IL in terms of degradation due to obtained voltage.

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Therefore, in this study, the objectives would be to (1) identify the electrochemical
stability window of 10 ppm [EMIM][N(Tf)2] by using electro-oxidation method with

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iron (Fe) electrode in different voltage (1V, 2V, 4V, 6V, 8V & 10V) with the amount
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respect of time (5 min, 10 min, 15 min, 30 min, 60 min), (2) characterize the chemical
structure of treated [EMIM][N(Tf)2] IL and (3) evaluate the feasibility of applying
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[EMIM][N(Tf)2] IL for Dye Sensitized Solar Cell (DSSCs) application based on
qualitative and quantitative analysis. The optimal voltage range to minimized
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instability of ionic liquid electrolyte was also investigated.

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2.0 Materials and Methodology

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2.1 Materials
1-ethyl-3-2-methylimidazolium bis (trifluoromethyl sulfonyl) imide or
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[EMIM][N(Tf)2] ionic liquid with molecular weight of 391.31 g/mol was selected as
an electrolyte and purchased from Sigma-Aldrich with purity of ≥98% based on (H-
NMR) analysis. Nitric acid of 65% (v/v) with density of 1.39 g/cm3 was purchased
from Merck Millipore which was used to clean and remove the metal oxide layer of
the electrode plates. Sodium Chloride (NaCl) with molar mass of 40.0 g/mol was
purchased from Merck Millipore is used as a bridge salt in the electrochemical cell.

2.2 Electrolyte Preparation

The IL [EMIM][N(Tf)2] with 10 ppm was prepared in aqueous form by
dissolving in distilled water with working volume of 200 ml. After [EMIM][N(Tf)2]
IL was prepared, 1 g of NaCl (or 5000 ppm) was poured into the solution in order to
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produce the current within the cell . Furthermore, it is worth to mention that, low
concentration of ionic liquid is used because even in small amount, degradation would
not occur with high voltage and ILs will be used as the supporting electrolytes for
DSSCs. It is as reported by Gu et.al. (2017) which stated that the concentration of KI
and I2 make negligible changes to the open-circuit voltage (Voc) of DSSC [25].

2.3 Electro-oxidation setup

For this experiment, direct current (DC) power supply was used to supply DC
potential to the wastewater sample to promote oxidation process. Crocodile clip was
placed at the electrodes and magnetic stirrer was used to agitate the solution

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throughout the experiment. Filter paper was used to remove any solid particles or

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sludge from the solution to avoid inaccuracy of reading for analysis purpose. The
electro-oxidation experimental setup was illustrated in Figure 1 and the operating
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condition was shown in Table 1.
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Figure 1: The electro-oxidation experimental setup

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Table 1. Operating conditions for electro-oxidation experiment with 1.0 g NaCl as

electrolyte.

No Voltage Concentration of Treatment time pH(a) Temperature

(V) [EMIM][N(Tf)2] (ppm) (min) (°C)

1 1
2 2
5, 10, 15, 30 and
3 4 10 7 25
60
4 6
5 8
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6 10
a)
Operated at ambient condition
2.4 Electro-oxidation
The experiment was conducted in a 250 mL batch reactor cell (Beaker) with
working volume of 250 ml. First, the aqueous [EMIM][N(Tf)2] IL solution was
poured into the beaker and iron (Fe) electrodes were halfly immersed into the solution.
Next, the electrodes were clipped with the crocodile clip in order to connect with the
DC power supply. The IL solution in the batch reactor was stirred continuously at 150
RPM during the experiment. There were six operating conditions: 1 V, 2 V, 4 V, 6 V,
8 V & 10 V. For each voltage, the time was set at 5, 10, 15, 30 and 60 min. The

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treated samples were collected for each treatment time and stored in the cold room

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temperature of 10°C. Next, the samples were analysed by using High-Performance
Liquid Chromatography (HPLC), Fourier-Transform Infrared Spectroscopy (FT-IR)
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and Atomic Absorption Spectroscopy (AAS). Once the analysis complete, the
electrochemical stability of [EMIM][N(Tf)2] IL will be analyzed to observe its
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degradation and decomposition of each treatment time.
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2.5 Degradation Analysis

There are three main equipment used for treated samples analysis which are
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High-Performance Liquid Chromatography (HPLC), Fourier-Transform Infrared

Spectroscopy (FT-IR) and Atomic Absorption Spectroscopy (AAS). The degradation
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degree of ionic liquids was measured by high-performance liquid chromatography

(HPLC, Agilent 1200) equipped with a reverse-phase C18 analytical column (Zorbax
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SB-C18). A water–acetonitrile mixture (25: 75, v/v) was used as the mobile phase.
The flow rate was set at 1 mL min−1 and 5 μL of inject volume was injected. The
retention time of the sample was taken for 3 minutes. Moreover, FTIR analysis was
used to identify the unknown functional group materials and confirmation of
production materials as compared with the standard peak. As for the AAS analysis, it
is used to measure the concentration of the chemical element and detect any presence
of metal in the ILs solution after electro-oxidation process by using flame atomic
absorption method with measurement time of 5 seconds. The pretreatment of the
sample sludge was treated before being analyzed by using HCl: HNO3 (3:1 ratio) into
1 g of dried sludge sample contained in crucible porcelain [26]. The mixture was then
heated and digested at 250°C in silicon oil bath until the solution became transparent.
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3.0 Results and Discussion

As shown in Figure 2, it represented the changing of bulk solution (two layers
were formed) of each treatment time which are 5, 10, 15, 30 and 60 min respectively.
The sludge were able to be separated and coagulated on the top layer as the bubble of
hydrogen gas causes the sludge to float to the top surface and the transparent bulk
solution remain at the bottom layer. The obtained sludge were then analyzed with
AAS to determine the iron metal content in the treated sample solution.

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Figure 2: Electrochemical oxidation process for each treatment time

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3.1 HPLC Analysis

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Figure 3(a) shows the concentration change of initial 10 ppm of

[EMIM][N(Tf)2] ionic liquid while Figure 3(b) illustrates the chromatogram peaks of
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each condition. After treated samples were analyzed, the concentration has slightly
changed approximately about 10 % from the initial 10 ppm as shown in Figure 3(c).
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On the other hand, in few conditions, the concentration fluctuated. Additionally, the
chromatogram peaks of each conditions in Figure 3(b) depicts the slightly degradation
of [EMIM][N(Tf)2] ionic liquid and some unknown components by comparing with
the standard curve in Figure 3(a). The unknown components in Figure 3(b) is most
probably identified as NO3− which occured due to the oxidation and opening of
imidazolium ring [27]. The chemical mechanism for degradation of 1-Ethyl-3-
Methylimidazolium was illustrated in Figure 4. As reported by Gao et.al (2014), there
are three possible degradation pathways as illustrated in Figure 4. Firstly, at (a), the
oxidization of 2,4,5 positioned H atoms of 1-ethyl-3-methylimidazolium ring to
generate the intermediate of 1-ethyl-3-methyl-2,4,5-trioxoimidazolidine ; Secondly, at
(b) the cleavage of N1-C2 and C4-C5 bonds in (a) occurred at once, such that the
 Journal Pre-proof 9

imidazolium ringwas opened, and degradation products (b) and (c) were detected; and
thirdly, further oxidation and cleavage of (b) and (c) to CH3COOH, CHOOH,NO2−,
and NO3− [27].

(a) (b)

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(c)
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Figure 3: HPLC results before and after treatment of [EMIM][N(Tf)2] IL based on (a)
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standard chromatogram curve of 10 ppm (b) combined HPLC chromatogram of each

voltages (c) concentration of treated [EMIM][N(Tf)2] IL at several voltages compared
with initial 10 ppm concentration
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Figure 4: Possible chemical mechanism for degradation of 1-Ethyl-3-

Methylimidazolium. Retrieved from [27].

In terms of degradation percentage, Table 2 illustrates the electrochemical

degradation of [EMIM][N(Tf)2] ionic liquid at 5 min and 60 min respectively. This is
to compare the degradation rate based on the shortest and longest amount of time
given. Basically, short period of time will contribute less formation of oxidizing agent
[28]. It can be seen that the degradation at 60th min has higher percentage compared
to degradation at 5th min. The highest degradation for 5th min is 4.626 % at 6V while,
degradation at 60th min is 8.427 % at 1 V. Theoretically, the increment of degradation

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percentage is directly proportional to the voltage [27]. The higher the voltage, the

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higher the degradation percentage which indicates that the highest degradation is
achieved at high amount of voltage supplied as high voltage enhanced anodic
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dissolution [29,30].
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Table 2: Degradation percentage of initial 10 ppm [EMIM][N(Tf)2] ionic liquid after
5 and 60 minutes.
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Potential (V) Degradation percentage (%)

5 min 60 min
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1V 0.740 8.476
2V 3.287 7.902
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4V 2.393 3.817
6V 4.626 6.075
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8V 0.110 3.507
10V 1.423 2.861

3.2 FTIR Analysis

FT-IR spectra of the treated [EMIM][N(Tf)2] IL samples are shown in Figure
5. It shows few peaks to specify the functional group of [EMIM][N(Tf)2] ionic liquid.
The FT-IR results shows that the trend of spectrum behave similar with the standard
curve of [EMIM][N(Tf)2] IL and slightly changed in term of transmittance percentage
within the same range of wavenumber. The possible functional groups which can be
identified from the treated samples are shown in Table 3.
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Figure 5: FT-IR stack curve analysis
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Table 3: Characteristic of treated sample IR absorption.
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Label Wavenumber,
1 cm- Bond Functional group

A 1650-1580 (m) N-H bend 1° amines

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3500-3200 (s, b) O-H stretch, H- alcohols, phenols

bonded
B 3400-3250 (m) N-H stretch 1°, 2° amines,
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amides
3300-2500 (m) O-H stretch carboxylic acids
3330-3270 (n,s) -C≡C-H:C-H alkynes
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stretch (terminal)
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3.3 AAS Analysis

Based on Figure 6, it shows that the Fe content in both liquid and sludge are
relatively high when the voltage is increased. For the liquid samples, the highest Fe
amount is at 10V-60 min with amount of 75.5 ppm. This is because high voltage
increases rapidly anodic dissolution which eventually causes a large release of ferric
ions into solution [31].
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Figure 6: Iron (Fe) concentration in various operating condition
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3.4 Factors that affect high electrochemical stability of [EMIM][N(Tf)2] ionic
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liquid
Based on the promising HPLC and FT-IR result as refer to Figure 3 and Figure
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5, Li et al. (2016) investigated that there are several effects of electrochemical

stability of imidazolium based which include [EMIM][N(Tf)2] ionic liquid: (1) The
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effect of alkyl chain length on electrochemical potential windows (EPW) of

imidazolium based ionic liquids, (2) The effect of cation on the EPW and (3) The
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effect of anion on the EPW [17].

For the effect of alkyl chain length, the degree of stability is high when the
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alkyl chain length of the cation is increased, which is consistent with the literature
[32]. Moreover, as for the effect of cation on the EPW, the [EMIM] + cation influences
the electrochemical stability of imidazolium based ionic liquid in terms of the
interaction between cation and anion which plays an important role. The interactions
of hydrogen bonding, hydrophilic interaction and ion-ion interaction may also involve
[33]. Furthermore, the stability of imidazolium based ionic liquid is because of the
lone pair orbitals of nitrogen accepts the extra electron upon reduction as well as the
molecule maintains aromatic due to 4+2π electron [34]. As for the effect of anion on
EPW, Li et. al. (2016) investigated that the amide anion [N(Tf)2]- is oxidized at
relatively high anodic potentials, which implies the broad stability of ionic liquid
based on this particular anion [17].
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4.0 Conclusion
Electrochemical stability of IL plays a crucial role for any application in
electrochemical processing which includes DSSCs. The results of this research have
been identified based on quantitative and qualitative analysis. FT-IR result shows that
there is slight degradation in the concentration amount of [EMIM][N(Tf) 2] IL which
is almost negligible and there is no change in spectrum as well as functional group
when compared with standard curve of [EMIM][N(Tf)2] IL from 1V to 10V. While
for HPLC result, it is found that overall degradation percentage in all condition is
approximately from 3-8 %. The production of Iron (Fe) content in sludge sample was

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higher than the liquid sample. Moreover, the highest Iron (Fe) amount was 224.45

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ppm at the condition of 6V at 5 min. These promising results prove that
[EMIM][N(Tf)2] IL has high electrochemical stability under high voltage supply. It is
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a suitable IL for DSSCs application since there is no changes towards the chemical
structure and concentration of samples. The higher the electrochemical stability of
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electrolyte, the better the lifetime and efficiency to produce electricity.
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Acknowledgement
The research was supported by Chemical Engineering department, Universiti
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Teknologi PETRONAS.
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Author Statement
Alif-Lohmoh: Investigation, Writing- Original draft preparation. Hakim
Wirzal: Conceptualization, Writing- Reviewing and Editing, Supervision. Syakinah Abd
Halim: Data curation, Writing- Reviewing and Editing Syaamil Saad: Methodology,
Writing- Reviewing and Editing. Yee Foong: Conceptualization , Validation.

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Conflict of Interests
The authors declare no conflicts of interest

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Highlights
 Ionic liquid as an exceptional choice for organic-based electrolyte in DSSC.
 Electro-oxidation method to evaluate the degradation of [EMIM][N(Tf)2].
 Electrochemical stability of [EMIM][N(Tf)2] with respect to high voltage.

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