processes
Review
Thermal Stability of Ionic Liquids: Current Status and
Prospects for Future Development
Chenqian Xu and Zhenmin Cheng *






Citation: Xu, C.; Cheng, Z. Thermal
Stability of Ionic Liquids: Current
Status and Prospects for Future
Development. Processes 2021, 9, 337.
https://doi.org/10.3390/pr9020337
Academic Editor: Andrew S. Paluch
Received: 22 January 2021
Accepted: 9 February 2021
Published: 12 February 2021
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
published maps and institutional affil-
iations.
Copyright: © 2021 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Processes 2021, 9, 337. https://doi.org/10.3390/pr9020337
State Key Laboratory of Chemical Engineering, School of Chemical Engineering,
East China University of Science and Technology, Shanghai 200237, China; chenqianxuci@gmail.com
* Correspondence: zmcheng@ecust.edu.cn; Tel.: +86-21-64253529
Abstract: Ionic liquids (ILs) are the safest solvent in various high-temperature applications due to
their non-flammable properties. In order to obtain their thermal stability properties, thermogravimet-
ric analysis (TGA) is extensively used to analyze the kinetics of the thermal decomposition process.
This review summarizes the different kinetics analysis methods and finds the isoconversional meth-
ods are superior to the Arrhenius methods in calculating the activation energy, and two tools—the
compensation effect and master plots—are suggested for the calculation of the pre-exponential factor.
With both parameters, the maximum operating temperature (MOT) can be calculated to predict the
thermal stability in long-term runnings. The collection of thermal stability data of ILs with divergent
cations and anions shows the structure of cations such as alkyl side chains, functional groups, and
alkyl substituents will affect the thermal stability, but their influence is less than that of anions. To
develop ILs with superior thermal stability, dicationic ILs (DILs) are recommended, and typically,
[C4 (MIM)2 ][NTf2 ]2 has a decomposition temperature as high as 468.1 ◦ C. For the convenience of ap-
plication, thermal stability on the decomposition temperature and thermal decomposition activation
energy of 130 ILs are summarized at the end of this manuscript.
Keywords: ionic liquid; thermal stability; thermal decomposition kinetics; dicationic ionic liquid
1. Introduction
Ionic liquids (ILs) are molten salts at room temperature composed of organic cations
and organic/inorganic anions [1,2]. ILs have been described as “designer solvents” because
their physicochemical property can be regulated or tailor-made by changing their con-
stituents or the structures of the pairs of the ions [3–5]. Previous research has proved that
ILs have many advantages, including non-volatility, non-flammability, high thermal and
chemical stability, wide electrochemical window, tunable miscibility, and good extraction
capability, which are not attained for the volatile organic solvents [6–8]. As a result of these
features and advantages, ILs are used in a wide range of applications such as catalyst [9–14],
pre-treatment of biomass [15–17], absorbent [18–20], gas sensors [21], electrolyte [22–24],
and membrane separation [25–27]. Among all of the applications, high-temperature utiliza-
tion accounts for the vast majority, including high-temperature lubricants [28–30], solvents
for high-temperature organic reactions [31], heat-transfer fluids [32,33], and thermal energy
storage [34,35]. Although ILs are generally considered to be thermally stable, yet their
stability is influenced seriously by a lot of factors.
So far, the thermal stability of ILs has been studied by many techniques, such as UV
(ultraviolet)–vis spectroscopy [36], flame ionization detection (FID) [37,38], and mass spec-
trometry (MS) [39–41]. Moreover, in some studies, ILs are heated isothermally in a furnace
and open to air to simulate the real environment [42,43]. In order to quantitatively evaluate
the thermal stability of ILs, parameters accounting for short-term and long-term thermal
stability are obtained by thermogravimetric analysis (TGA), and the most representative
ones are the onset decomposition temperature Tonset and Tz/y (decomposition degree z
https://www.mdpi.com/journal/processes
Processes 2021, 9, 337 2 of 36

in a selected time y), respectively. Although many studies have indicated Tonset obtained
by dynamic TGA overestimates the thermal stability [36,39,44], it is still widely used to
express the stability of ILs from divergent papers [45,46]. Despite the long-term isothermal
experiments can more accurately reflect the real stability of ILs [44,47–49], but it should
be noted that the time in these experiments is still far less than the heat exposure time in
many real applications. To provide the method in predicting long-term thermal stability,
different models have been developed [50–52].
To solve the problem when the entire sample cannot be decomposed [47,48], non-
isothermal TGA is developed as the most popular method to determine the kinetic pa-
rameters in the thermal decomposition process, and the combination of TGA data allows
researchers to calculate the activation energy and pre-exponential factor in this process.
Arrhenius methods are widely used in kinetics analysis due to their simple calculation
process. However, some recent studies have used the isoconversional methods to calculate
the activation energy [44,53,54], while the methods of compensation effect and master plots
provide the pre-exponential factor calculation [55–57].
The thermal stability of ILs is mainly determined by the structure of anions and
cations, and anions usually play a major role [46,58,59]. However, more studies are focused
on the modification of cations, including alkyl chain length, functional groups, and alkyl
substituents to improve the thermal stability of ILs [60,61]. Other conditions, such as gas
atmosphere, heating rates, and impurities, also influence the thermal stability measure-
ments [45,62]. Among which, the heating rate has the most significant impact on the TGA
results, and the difference in Tonset obtained at 1 ◦ C/min and 20 ◦ C/min is even up to
100 ◦ C [44]. Finally, ILs mixtures and dicationic ILs (DILs) are introduced as potential
applications for the further development of high-temperature ILs.

2. Measurement of Thermal Stability

2.1. Short-Term Thermal Stability
Dynamic TGA is applied in the study for short-term thermal stability measurement,
and the most common heating rate is 10 ◦ C/min [36,39,42,63–66]. Effects of different
heating rates, at 5, 10, 15, 20 ◦ C/min are available in previous studies, and it should be noted
that the faster the heating rate is, the more overestimated the thermal stability of ILs is, and
the corresponding dynamic TGA curve will move to the right accordingly. [18,39,49,53,57].
Tonset , which is basically known as the short-term thermal stability, is determined by
dynamic TGA. Moreover, it is a value calculated by the thermal analysis software, which
is defined as the intersection of the baseline of zero weight loss and the tangent of the
weight versus temperature curve as decomposition occurs [45]. Therefore, the temperature
at which the sample begins to decompose is lower than Tonset . Tz (decomposition degree z)
is also a parameter to characterize the short-term thermal stability, which directly shows
the temperatures at different decomposition degrees [55,63,67–69]. Both parameters are
illustrated clearly in Figure 1. In fact, the difference between Tonset and T50% or T10% is
a measure of the decomposition rate, and the lower the temperature difference between
Tonset and T50% or T10% , the lower the stability of the ionic liquid [70].
 Processes2021,
Processes 2021,9,9,x337
FOR PEER REVIEW 33ofof36
36

Processes 2021, 9, x FOR PEER REVIEW 3 of 36

Figure
Figure1.1.Thermal parameters
Thermal of ionic
parameters liquids
of ionic (ILs)(ILs)
liquids obtained fromfrom
obtained dynamic thermogravimetric
dynamic thermogravimetric
analysis
analysis(TGA)
(TGA)curves
curves[70].
[70].

Another method to investigate the short-term thermal stability called derivative

thermogravimetry (DTG) is shown in Figure 2. It determines the temperature of maximum
degradation Tpeak [42,64,71–73], i.e., if there is one more peak in the DTG curve, the
temperature corresponding to the highest peak will be selected [74]. The number of peaks
Figure 1. Thermal
in a DTG parameters
curve is of ionic liquids
also an important (ILs) obtained
parameter. fromhave
Most ILs dynamic
onlythermogravimetric
one peak, indicating
analysis (TGA) curvesprocess
the decomposition [70]. is a simple one-step process [44], and two peaks in some DTG
curves correspond to two different degradation processes in the sample [63].

Figure 2. Derivative thermogravimetry (DTG) curves of [C4MIM][NTf2] [18].

2.2. Long-Term Thermal Stability

Although Tonset is widely used to describe the thermal stability of ILs, it is not a
suitable parameter for long-term industrial applications. To establish the correlation
between the operating temperature and time, it is necessary to investigate the long-term
thermal
Figure 2.
stability of thermogravimetry
ILs through isothermal
Derivative thermogravimetry
2. Derivative
TGAof[36,75,76].
(DTG) curves
curves of [C44MIM][NTf
In this[18].
MIM][NTf22]][18].
method, samples are
Figure (DTG) [C
heated at a fixed temperature varying from an hour to tens of hours, then Tz/y is
2.2. Long-Term
determined Thermal Stability
[49,57,77–79]. As shown in Figure 3, more than three temperatures are usually
2.2. Long-Term Thermal Stability
used in the analysis [75,78],
Although Tonset is widely andused
the interval between
to describe different
the thermal temperatures
stability of ILs, it isisnot
determined
a suitable
by Although T onset is widely used to describe the thermal stability of ILs, it is not a
Tonset [74].forHowever,
parameter long-termit industrial
is much shorter than the
applications. Tocycle of industrial
establish runnings.
the correlation Neither
between the
suitable parameter
extrapolating for long-term
experimental data nor industrial applications. To of establish theTGA correlation
operating temperature and time, it is extending
necessary tothe heating time
investigate isothermal
the long-term thermal seems
stability
between
to the operating temperature andmeans
time, it is necessary to investigate the long-term
ofbe the
ILs best
through solution.
isothermal Therefore, some
TGA [36,75,76]. predicting
In this method, thesamples
long-termare thermal
heated at stability
a fixed
thermal
oftemperaturestability
ILs have been of ILs
proposed.
varying through isothermal TGA [36,75,76]. In this method,
from an hour to tens of hours, then Tz/y is determined [49,57,77–79]. samples are
heated
As shown at in
a Figure
fixed temperature
3, more than three varying from an are
temperatures hour to tens
usually usedofinhours,
the analysisthen [75,78],
Tz/y is
determined
and the interval [49,57,77–79]. As shown
between different in Figure 3,ismore
temperatures than three
determined by temperatures are usually
Tonset [74]. However, it is
used in the analysis [75,78], and the interval between different temperatures
much shorter than the cycle of industrial runnings. Neither extrapolating experimental data is determined
by Tonset [74]. However, it is much shorter than the cycle of industrial runnings. Neither
extrapolating experimental data nor extending the heating time of isothermal TGA seems
to be the best solution. Therefore, some means predicting the long-term thermal stability
of ILs have been proposed.
 Processes 2021, 9, 337 4 of 36

Processes 2021, 9, x FOR PEER REVIEW 4 of 36

nor extending the heating time of isothermal TGA seems to be the best solution. Therefore,
some means predicting the long-term thermal stability of ILs have been proposed.

Figure 3. Isothermal TGA for (a) 4-methyl-1-propyl-1,2,4-triazolium iodide, (b) 4-methyl-1-propyl-1,2,4-triazolium triflate,
Figure 3. Isothermal
and (c) TGA for (a) 4-methyl-1-propyl-1,2,4-triazolium
1-butyl-4-methyl-1,2,4-triazolium iodide,[75,78].
[NTf2 ] in nitrogen atmosphere (b) 4-methyl-1-propyl-1,2,4-triazolium triflate,
and (c) 1-butyl-4-methyl-1,2,4-triazolium [NTf2] in nitrogen atmosphere [75,78].
Seeberger et al. [50] proposed using the maximum operating temperature (MOT) to
Seeberger
measure et al. [50] proposed
the long-term using the
thermal stability maximum
at 1% operating
decomposition temperature
degree, which is(MOT) to
measure the long-term thermal stability at 1% decomposition degree, which is
E
MOT = 𝐸 (1)
MOT = R·[4.6 + ln( A·tmax )] (1)
𝑅 ∙ 4.6 + 𝑙𝑛(𝐴 ∙ 𝑡 )
where A denotes the pre-exponential factor, E is the activation energy, R is the universal
where 𝐴 denotes the pre-exponential factor, 𝐸 is the activation energy, 𝑅 is the
gas constant, and tmax is the maximum operation time. MOT has been used to predict
universal gas constant, and 𝑡 is the maximum operation time. MOT has been used to
the long-term thermal stability successfully in several recent studies [56,71,73]. Moreover,
predict the long-term thermal stability successfully in several recent studies [56,71,73].
MOT is also applied in the prediction of the thermal stability of ILs mixtures [80].
Moreover, MOT is also applied in the prediction of the thermal stability of ILs mixtures
To estimate the maximum time for ILs used under a specific temperature, Salgado et al. [51]
[80].
proposed an exponential function of the temperature, similar to Cao and Mu [74], which is
To estimate the maximum time for ILs used under a specific temperature, Salgado et
al. [51] proposed an exponential function of t =the
Betemperature,
CT similar to Cao and Mu [74],(2)
which is
where t is the time in minutes, B and C are the fitting parameters, and T is the scanning
𝑡 = 𝐵𝑒 (2)
temperature in K. From isothermal TGA, t, that each IL takes to decompose to a certain
where 𝑡 is the
percentage of mass, minutes, 𝐵at different
time isindetermined and 𝐶 are the fitting
T. This equation parameters, and 𝑇 describe
can quantitatively is the
scanning temperature
the relationship in K. the
between From isothermal TGA,
decomposition 𝑡, that each
temperature and IL
thetakes to decompose
decomposition time toof
a ILs
certain
underpercentage of mass,
a certain degree is determinedWith
of decomposition. at this
different
method, 𝑇 . TThis
0.01/10hequation
, T0.05/10hcan
, and
T0.1/10h havedescribe
quantitatively been correlated, and T0.01/10h
the relationship betweenwas the
given by Wooster ettemperature
decomposition al. [52] according
and the to
decomposition time of ILs under a certain degree of decomposition. With this method,
T0.01/10h, T0.05/10h, and T0.1/10h have beenT0.01/10h ≈ 0.82T
correlated, and 6=0) was given by Wooster et al.(3)
T0.01/10h
(dw/dT
[52] according to
where T(dw/dT 6=0) is the temperature at which the first appreciable weight loss occurs. The
results of T0.01/10h calculated by𝑇Equation . / ≈ 0.82𝑇
(2) is (higher
/ than
) that by Equation (3), which (3)
where 𝑇( / ) is the temperature at which the first appreciable weight loss occurs. The
results of 𝑇 . / calculated by Equation (2) is higher than that by Equation (3), which
 Processes2021,
Processes 2021,9,9,337
x FOR PEER REVIEW 55of
of36
36

attributes to the different experimental conditions [51]. In another research, the above
attributes to the different experimental conditions [51]. In another research, the above three
three methods are used to calculate 𝑇 . / of some aprotic ILs [63]. The experiments
methods are used to calculate T0.01/10h of some aprotic ILs [63]. The experiments prove
prove that the results obtained by Wooster’s method (Equation (3)) are the highest,
that the results obtained by Wooster’s method (Equation (3)) are the highest, followed by
followed by Salgado’s method (Equation (2)), and those calculated by Seeberger’s method
Salgado’s method (Equation (2)), and those calculated by Seeberger’s method (Equation (1))
(Equation
are (1)) are the lowest.
the lowest.
2.3. Factors
2.3. Factors Affecting
Affecting TGA
TGA Results
Results
2.3.1. Heating
2.3.1. Heating Rates
Rates
In dynamic
In dynamic TGA, TGA,TTonset
onset varies significantly with different heating heating rates,
rates, since
since when
when
the temperature rises rapidly, it will easily exceed the onset decomposition
the temperature rises rapidly, it will easily exceed the onset decomposition temperature, temperature,
resulting
resulting inin aa mass
mass loss
loss that
that cannot
cannot be be measured
measured correctly
correctly [50].
[50]. As shown in Figure 4, 4,
compared
compared with a slower slower heating
heatingrate, rate,the
thehigher
higherTonset
Tonset is obtained
is obtained at aatfaster
a faster heating
heating rate
rate
[57].[57].
For For
[C2[C 2 MIM][NTf
MIM][NTf 2 ] and
2] and [C3[C 3 MIM][NTf
MIM][NTf ], is
2], 2it it isfound
foundthat
that the
the difference
difference ofofTonset
Tonset
obtained ◦ C/min and 20 ◦ C/min is 100 ◦ C [44]. This trend
obtainedat at11 °C/min 20 °C/min is 100 °C [44]. This trend has also been been found
found inin more
more
investigations
investigations [39,54].
[39,54]. Therefore,
Therefore, itit is is necessary
necessary toto pay
pay attention
attention to
to the
theheating
heatingrateratewhen
when
comparing T
comparing Tonset by different
onset by different authors. As a criterion, most of the literature
literature known to
known todate
date
gives ◦ C/min.
gives the
the TTonset value at
onset value at 10
10 °C/min.

[C2MIM][Cl]
280
[C4MIM][Cl]
[C6MIM][Cl]
[C10MIM][Cl]
270
Tonset (℃)

260

250

240

230
5 10 15 20

Heating rates (℃/min)

4. TTonset
Figure 4.
Figure measuredat
onset measured atdifferent
different heating
heating rates
rates [57].
[57].

2.3.2.
2.3.2. Gas
Gas Atmosphere
Atmosphere
N
N2 is often
2 is often chosen
chosen as
as the
the gas
gas atmosphere
atmosphere in in TGA,
TGA, while
while itit is
is just
just aa special
special case
case in
in
industrial applications. Therefore, it is necessary to figure out the influence
industrial applications. Therefore, it is necessary to figure out the influence of different of different
gas atmospheres on the thermal stability of ILs. As shown by Götz et al., the TGA results
gas atmospheres on the thermal stability of ILs. As shown by Götz et al., the TGA results
of [P14,6,6,6 ][NTf2 ] indicate the mass loss in H2 is much higher than that in N2 at the same
of [P14,6,6,6][NTf2] indicate the mass loss in H2 is much higher than that in N2 at the same
temperature, i.e., H2 accelerates the decomposition of [P14,6,6,6 ][NTf2 ] [6]. Figure 5 shows
temperature, i.e., H2 accelerates the decomposition of [P14,6,6,6][NTf2] [6]. Figure 5 shows
some Tonset and T10% obtained in both N2 and O2 atmospheres. The results reveal that
some Tonset and T10% obtained−in both N2 and O2 atmospheres. The◦ results reveal that the
the Tonset and T10% of [NTf ] ILs obtained in O2 are lower by 38 C to 97 ◦ C than those
Tonset and T10% of [NTf2]－- ILs2 obtained in O2 are lower by 38 °C to 97 °C than those obtained
obtained in N2 , indicating the reactive atmosphere reduces their thermal stability [49]. The
in nitrogen, indicating the reactive atmosphere reduces their thermal stability [49]. The
effect of air on thermal stability is similar to that of O2 . As shown in Figure 6, [P4,4,4,8 ][BScB]
effect of air on thermal stability is similar to that of O2. As shown in Figure 6, [P4,4,4,8][BScB]
and [P4,4,4,8 ][BMB] are more thermally stable in N2 than in air [81], and the same results are
and [P4,4,4,8][BMB] are more thermally stable in N2 than in air [81], and the same results are
observed in another study [55]. However, according to Figure 7, the Tonset of some choline,
observed in another study [55]. However, according to Figure 7, the Tonset of some choline,
pyridinium, and phosphonium ILs are not significantly affected by gas atmospheres, and
piperidine,
the maximum and phosphonium
temperature ILs areisnot
difference significantly
only affected by gas atmospheres, and
26 ◦ C [40,73].
the maximum temperature difference is only 26 °C [40,73].
 Processes 2021, 9, x FOR PEER REVIEW 6 of 36
Processes 2021, 9, 337 6 of 36
Processes 2021, 9, x FOR PEER REVIEW 6 of 36

Figure 5. Tonset and T10% of [NTf2]－ ILs in N2 and O2 at a heating rate of 10 °C/min [49].

5. TT and T10%－ − ILs in N and O at a heating rate of 10 ◦ C/min [49].

Figure 5.Figure
Tonset and 10% of
onset [NTf2] of [NTf
ILs 2 ]2 and
in N O2 at2a heating
2 rate of 10 °C/min [49].

Figure 6. Tonset of [P4,4,4,8 ][BScB] and [P4,4,4,8 ][BMB] in N2 and air at a heating rate of 10 ◦ C/min [81].
Figure 6. Tonset of [P4,4,4,8][BScB] and [P4,4,4,8][BMB] in N2 and air at a heating rate of 10 °C/min [81].

Figure 6. Tonset of [P4,4,4,8][BScB] and [P4,4,4,8][BMB] in N2 and air at a heating rate of 10 °C/min [81].
 Processes 2021, 9, x FOR PEER REVIEW 7 of 36
Processes 2021, 9, 337 7 of 36

Figure 7. Tonset of choline, pyridinium, and phosphonium ILs in N2 and air at a heating rate of
Figure 7. Tonset of choline, pyridinium, and phosphonium ILs in N2 and air at a heating rate of 10
10 ◦ C/min [40,73]. Reproduced with permission from Clio Deferm, Physical Chemistry Chemical
°C/min [40,73]. Reproduced with permission from Clio Deferm, Physical Chemistry Chemical
Physics; published
Physics; published by Royal by Royal
SocietySociety of Chemistry,
of Chemistry, 2018;with
2018; reproduced reproduced
permission with
from permission from J.J.Parajó,
J.J.Parajó,
The Journal The Journal of Chemical
of Chemical Thermodynamics; published
Thermodynamics; published bybyElsevier, 2020. 2020.
Elsevier,
2.3.3. Impurities
2.3.3. Impurities
In most cases, water has a wide range of values from 30 ppm to 21,000 ppm [51,66,73].
In most
For different cases,
kinds water
of ILs, has
water hasadifferent
wide range effectsofonvalues from 30
their thermal ppm On
stability. to 21,000
one ppm [51,66,73].
For different
hand, water hinders kindstheof ILs, water
degradation has different
reaction effects
of [C2MIM][Ac] on[Ctheir
and thermal
4MIM][Ac], stability. On one hand,
as shown
by Williams
water et al. that
hinders thethe mass of [C2MIM][Ac]
degradation reaction and of[C[C
4MIM][Ac]
2 MIM][Ac] decreased
and significantly
[C4 MIM][Ac], as shown by
in an isothermal
Williams et al. TGA
that atthe150mass
°C, but the MIM][Ac]
of [C time-lapsed and changed [C in the UV–vis
MIM][Ac] spectra
decreased significantly in
2 4
monitored over 24 h showed that ◦ mixtures of [C2MIM][Ac] and [C4MIM][Ac] with water
an isothermal TGA at 150 C, but the time-lapsed changed
did not display any significant decomposition at 150 °C [36]. The observed results are in
in the UV–vis spectra monitored
over 24 h showed that mixtures
line with the research of [C2MIM][AcO] and [C4MIM][AcO]of [C 2 MIM][Ac] and [C MIM][Ac]
[82]. On the4 other hand, the with water did not
Tdisplay
onset of the quaternary phosphonium carboxylate ILs ◦
any significant decomposition at 150 C [36]. The observed results are in line with
decreases by 19.8 °C at most when
the
thewater contentofis[C
research saturated, as shown in Figure 8 [83]. Moreover, the TGA curves of
2 MIM][AcO] and [C4 MIM][AcO] [82]. On the other hand, the Tonset
two protic ILs, [DEMA][HSO4] and [DEMA][CF3COO], decrease markedly with ◦the
of the quaternary phosphonium carboxylate ILs decreases by 19.8 C at most when the
increase of water content [84]. However, for [C1OC2C1Py][NTf2], [C1OC2C1Py][(C2F5)3PF3],
water content
and [P6,6,6,14 ][(C2F5)is saturated, as shown in Figure 8 [83]. Moreover, the TGA curves of two
3PF3], differences of Tonset between water saturation and supply

protic ILs,
conditions are[DEMA][HSO 4 ] and [DEMA][CF
lower than the expanded uncertainties of3theCOO], decrease
apparatus [63]. markedly with the increase
In addition
of water content to water,
[84].the influence for
However, of inorganic
[C1 OC2salts and metal2 ],oxides
C1 Py][NTf [C1 OC on 2thermal
C1 Py][(C2 F5 )3 PF3 ], and
stability has also been studied. Adding CuO to [C2MIM][Ac] results in an exothermic
Processes 2021, 9, x FOR PEER REVIEW
[P 6,6,6,14 ][(C F
2 5 3 ) PF 3 ], differences of T onset between water saturation and supply conditions
8 of 36
reaction and lowers the decomposition temperature. It is assumed that CuO decomposes
are lower
ester compounds thanproduced
the expanded uncertainties
from [C2MIM][Ac] of the
as it might apparatus
accelerate [63].
the decomposition of
organic compounds [85]. In addition, results summarized in Figure 9 show Tonset of bulk
ILs are significantly higher than the Tonset of γ-Al2O3-supported ILs, indicating the
interactions of ILs with γ-Al2O3 control their thermal stability limits [58]. Putting 20%
NH4Cl into [BMMIM][Cl] reduces the thermal stability [86], and Tonset of commercial
[P6,6,6,14][Cl] is 8 °C lower than its pure counterpart [40]. Both studies mean the existence of
impurities alters the thermal stability of ILs.

Figure
Figure8. 8.
TonsetTand
onsetT10%
andof neat
T10%ILsof
andneat
mixtures
ILs with
andwater at a heating
mixtures withrate of 5 °C/min
water in
at a heating rate of 5 ◦ C/min in
nitrogen atmosphere [83].
nitrogen atmosphere [83].
Processes 2021, 9, 337 8 of 36

In addition to water, the influence of inorganic salts and metal oxides on thermal
stability has also been studied. Adding CuO to [C2 MIM][Ac] results in an exothermic
reaction and lowers the decomposition temperature. It is assumed that CuO decomposes
ester compounds produced from [C2 MIM][Ac] as it might accelerate the decomposition
of organic compounds [85]. In addition, results summarized in Figure 9 show Tonset of
bulk ILs are significantly higher than the Tonset of γ-Al2 O3 -supported ILs, indicating the
interactions of ILs with γ-Al2 O3 control their thermal stability limits [58]. Putting 20%
NHT
Figure 8. Tonset and 4 Cl into
10% of [BMMIM][Cl]
neat reduces
ILs and mixtures the thermal
with water stability
at a heating rate of 5[86], andinTonset of commercial
°C/min
[P6,6,6,14
nitrogen atmosphere ][Cl] is 8 ◦ C lower than its pure counterpart [40]. Both studies mean the existence
[83].
of impurities alters the thermal stability of ILs.

Figure 9. Tonset of Bulk and γ-Al2 O3 -supported ILs at a heating rate of 10 ◦ C/min in nitrogen atmosphere [58].
Figure 9. Tonset of Bulk and γ-Al2O3-supported ILs at a heating rate of 10 °C/min in nitrogen
atmosphere [58].
3. Kinetics of Thermal Decomposition
The kinetic
3. Kinetics of Thermal data in the thermal decomposition process can be obtained based on
Decomposition
isothermal and non-isothermal TGAs. Generally, the rate of thermal decomposition can be
The kinetic data in the thermal decomposition process can be obtained based on
expressed by the following formula:
isothermal and non-isothermal TGAs. Generally, the rate of thermal decomposition can
be expressed by the following formula: dα/dt = k( T )· f (α) (4)
𝑑𝛼/𝑑𝑡 = 𝑘(𝑇) ∙ 𝑓(𝛼) m − m (4)
0
α= (5)
𝑚 −𝑚 m0 − m1
𝛼= (5)
𝑚 f−(α𝑚
where k ( T ) is the rate constant, ) is determined by the kinetic models as shown in
Table 1, and m0 , m, and m1 are the initial mass, mass at certain time, and terminal mass of
where 𝑘(𝑇) is the rate constant, 𝑓(𝛼) is determined by the kinetic models as shown in
the sample, respectively. α is defined as the fraction of the total mass loss in the process,
Table 1, and 𝑚 , 𝑚, and 𝑚 are the initial mass, mass at certain time, and terminal mass
ranging from 0 (no mass loss) to 1 (complete mass loss).
of the sample, respectively. 𝛼 is defined as the fraction of the total mass loss in the
process, ranging from 0 (no mass loss) to 1 (complete mass loss).
Table 1. Some of the models used in thermal decomposition kinetics of ILs. (n 6= 1).

Reaction Model Code f(α)

Power law P2 2α1/2
Power law P3 3α2/3
One-dimensional diffusion D1 1/2α−1
Two-dimensional diffusion D2 [−ln(1 − α)]−1
Three-dimensional diffusion D3 3/2(1 − α)2/3 [1 − (1 − α)1/3 ]−1
Zero-order F0 1
First-order F1 1−α
nth order Fn (1 – α)n

The correlation between the rate constant and the temperature is defined by the
Arrhenius equation as  
E
k( T ) = A· exp − (6)
RT
Processes 2021, 9, 337 9 of 36

where A denotes the pre-exponential factor, E is the activation energy, R is the universal
gas constant, and T refers to the temperature.
Combining Equation (4) and Equation (6) yields
 
E
dα/dt = A· exp − · f ( α ). (7)
RT

If the heating rate β is constant, then Equation (7) can be transformed into Equation (8)
as follows:  
E
β(dα/dt) = A· exp − · f (α) (8)
RT
The calculation of Arrhenius parameters, E and A, will be introduced in the following sections.

3.1. Isoconversional Methods

The isoconversional methods are based on the isoconversional principle, meaning
that the reaction rate dα/dt is only a function of temperature at a constant extent of
conversion [41] and the reaction model f (α) is independent of temperature [87]. In addition,
these methods require that the decomposition process can be approximated as a single-step
kinetic process, that is to say, activation energy calculated by isoconversional methods
does not vary significantly with α [88]. According to this principle, the isoconversional
values of activation energy Eα can be evaluated without assuming or determining any
particular form of the reaction model, so the isoconversional methods are frequently called
“model-free” methods. Currently, these methods have been classified into differential
isoconversional methods and integral isoconversional methods.

3.1.1. Differential Isoconversional Methods

Taking the logarithm on both sides of Equation (8), the most representative differential
isoconversional method is obtained according to Friedman [89]
h i Eα
ln β i (dα/dt)α,i = ln[ f (α) Aα ] − (9)
RTα,i

where the subscript i denotes individual heating rate, and Tα,i is the temperature at which
the extent of conversion α is reached under ith heating rate. The activation energy corre-
sponding to each conversion α can be obtained easily by using DTG and TGA data. As
shown in Figure 10, in order to better characterize the thermal decomposition process of
[C4 MIM][PF6 ] in the nitrogen atmosphere, the thermal decomposition is divided into two
steps. The activation energy value calculated by the Friedman method suggests that the
linearity of the result is relatively poor in the fitting process and the activation energy
varies significantly with α [55]. In addition, a similar conclusion has also been drawn in
other investigations [90]. In the non-isothermal kinetic analysis of imidazolium [NTf2 ] ILs,
it is found that the activation energy calculated by the Friedman method has the largest
variation range [44].
 the linearity of the result is relatively poor in the fitting process and the activation energy
varies significantly with 𝛼 [55]. In addition, a similar conclusion has also been drawn in
Processes 2021, 9, 337 other investigations [90]. In the non-isothermal kinetic analysis of imidazolium [NTf102]ofILs,
36
it is found that the activation energy calculated by the Friedman method has the largest
variation range [44].

10. Linear Arrhenius plots for [C

Figure 10. [C44MIM][PF
MIM][PF6]6 ]ininaanitrogen
nitrogenatmosphere.(a),
atmosphere.(a),(b)
(b)Flynn–Wall–
Flynn–Wall–
method log β versus 1000/T; (c), (d) Coats–Redfern (CR) method ln(β/T2 ) versus
Ozawa (FWO) method log β versus 1000/T; (c), (d) Coats–Redfern (CR) method ln(β/T 2) versus

1000/T and; (e), (f)

1000/T and; (e), (f) Friedman method ln[β(dα/dt)]
Friedman method ln[β(dα/dt)] versus
versus 1000/T
1000/T[55].
[55].Reproduced
Reproducedwith
with permission
permission
from Zhen Huang, Journal of Thermal Analysis and Calorimetry; published by Springer
from Zhen Huang, Journal of Thermal Analysis and Calorimetry; published by Springer Nature, Nature,2019.
2019.

3.1.2. Integral
IntegralIsoconversional
isoconversionalMethods
methods
By integrating Equation
Equation (7),
(7), the
the following
following equation
equation can
can be
be obtained
obtained as
as

dα𝑑𝛼 = 𝐴 ∙ t exp −E𝐸 𝑑𝑡

Z α Z  
g(αg(𝛼)
)≡ ≡ = A · exp − 𝑅𝑇 dt
(10)
(10)
0 f (𝑓(𝛼)
α) 0 RT
In the
In the case
case of
of constant
constant heating
heating rate,
rate, Equation
Equation (10)
(10) can
can be
be converted
converted into
into
𝑑𝛼 𝐴Z 𝐸
g(𝛼)Z≡Tα dα =
A ∙ T exp − E 𝑑𝑇 (11)

g( α ) ≡ 𝑓(𝛼)
= 𝛽 · exp − 𝑅𝑇 dT (11)
0 f (α) β 0 RT
According to the isoconversional principle, Equation (10) can be converted into
According
Equation to the
(12) under theisoconversional
isothermal conditionprinciple, Equation (10) can be converted into
as follows:
Equation (12) under the isothermal condition as follows:
𝐸
lnt , = ln 𝑔(𝛼)/𝐴 + (12)
E𝑅𝑇
α
lntα,i = ln[ g(α)/Aα ] + (12)
RTi

where Ti indicates isothermal temperature, and tα,i is the time to reach a given extent of
conversion in the ith isothermal experiment. Apart from the study by Williams et al. that
used this method to calculate the activation energy and pre-exponential factor values of
Processes 2021, 9, 337 11 of 36

1-alkyl-3-methylimidazolium chloride ILs [57], no other literature is known using this

method to analyze the thermal degradation kinetics of ILs.
Compared with isothermal experiments, the constant heating rate (β = constant) is
more popular in isoconversional kinetic analysis [18,39,49,53,56,57]. There is no analytical
solution to the integral of Equation (11), so a series of integral isoconversional methods
using different approximations have appeared. Many integral isoconversional methods
can be expressed in the following form [91]:

B
 Eα
ln β i /Tα,i = Const − C (13)
RTα

Flynn–Wall–Ozawa (FWO) method [92,93], Kissinger–Akahira–Sunose (KAS) [94]

method, which is also known as Coats–Redfern (CR) method [95], and Starink method [96]
are all derived based on Equations (14)–(16), respectively. Then the activation energy values
can be calculated from the slope of plots.

Eα
ln( β i ) = Const − 1.052 (14)
RTα

2
 Eα
ln β i /Tα,i = Const − (15)
RTα

1.92
 Eα
ln β i /Tα,i = Const − 1.0008 (16)
RTα
Table 2 indicates that the activation energy difference of [C4 MIM][NTf2 ] calculated
by the KAS method, FWO method, and Starink method is less than 5.4 kJ/mol, and the
correlation coefficients (R2 ) is all greater than 0.97 [18]. The calculated results are in line with
many other studies [44,53,54]. Therefore, as recommended by ICTAC (the International
Confederation for Thermal Analysis and Calorimetry), there is no need to perform kinetic
analysis in multiple forms of integral isoconversional methods [88].

Table 2. Correlation coefficient and activation energy for the [C4 MIM][NTf2 ] calculated using
different integral isoconversional methods [18].

KAS FWO Starink

α
Eα /kJ mol−1 R2 Eα /kJ mol −1 R2 Eα /kJ mol −1 R2
0.1 109.5 0.99 114.6 0.99 109.9 0.99
0.2 116.9 0.99 121.9 0.99 117.3 0.99
0.3 121.6 0.99 126.5 0.99 122.0 0.99
0.4 121.3 0.99 126.4 0.99 121.7 0.99
0.5 120.3 0.99 125.6 0.99 120.7 0.99
0.6 116.7 0.99 122.2 0.99 117.1 0.99
0.7 112.2 0.97 118.0 0.98 112.6 0.97
0.8 108.8 0.97 114.9 0.97 109.2 0.97
Average 115.9 121.3 116.3

The numerical integration developed by Vyazovkin et al. improves the calculation

accuracy [97–99]. For a series of different heating rates, the activation energy values can be
obtained by minimizing the following function:
n n I ( Eα , Tα, i ) β j
φ( Eα ) = ∑∑ I

Eα , Tα, j β i
(17)
i =1 j 6 = i
Processes 2021, 9, 337 12 of 36

where the subscript i denotes different heating programs, and the subscript j is used to
denote all heating rates other than i. In order to reduce error as much as possible, the
temperature integral is calculated over a small segment [87] as
Z Tα
− Eα
 
I ( Eα , Tα, i ) = exp dt (18)
Tα−∆α RT

Table 3 shows that the activation energy values calculated by the Vyazovkin method
are similar to the results of the KAS and Starink methods, indicating that the latter two
simple integration methods are precise enough in most cases [55,57], and the Vyazovkin
method is a better choice when the activation energy values vary with α obviously [88].

Table 3. The activation energy (Eα ) values determined from the Kissinger–Akahira–Sunose (KAS)
method, Vyazovkin method, Starink method, and max-rate Starink method. Reproduced with
permission from Zhen Huang, Journal of Thermal Analysis and Calorimetry; published by Springer
Nature, 2019; reproduced with permission from Michael L.Williams, Thermochimica Acta; published
by Elsevier, 2020.

ILs Method Eα/kJ mol−1

77.52
Vyazovkin
101.22
[C4 MIM][PF6 ] [55]
76.83
KAS
100.60
Vyazovkin 120.8
[C2 MIM][Cl] [57]
Starink 121.6
Vyazovkin 151.5
[C3 MIM][Cl] [57]
Starink 155.0
Vyazovkin 146.8
[C4 MIM][Cl] [57]
Starink 150.8
Vyazovkin 98.6
[C6 MIM][Cl] [57]
Starink 97.9
Vyazovkin 148.2
[C10 MIM][Cl] [57]
Starink 149.7

3.1.3. Maximum-Rate Methods

When the maximum rate of decomposition of ILs is achieved, Tα in Equation (13)
can be replaced by Tpeak [91]. This class of methods will be indicated by adding “max
rate” before the name. In the max-rate Starink method, the activation energy of 1-alkyl-3-
methylimidazolium chloride can be calculated, which is similar to that calculated by the
Vyazovkin method and Starink method, as shown in Table 4 [57]. However, the activation
energy of [C4 MPy][NTf2 ] calculated by Tpeak is about 20 kJ/mol higher than that calculated
by Tα [53].
Processes 2021, 9, 337 13 of 36

Table 4. The activation energy values determined from the integral isoconversional methods and
maximum-rate methods. Reproduced with permission from Khurrum Shehzad Quraishi, Journal of
Thermal Analysis and Calorimetry; published by Springer Nature, 2017; reproduced with permission
from Michael L.Williams, Thermochimica Acta; published by Elsevier, 2020.

ILs Method Eα/kJ mol−1

Starink 121.6
[C2 MIM][Cl] [57]
Max-rate Starink 114.6
Starink 155.0
[C3 MIM][Cl] [57]
Max-rate Starink 155.6
Starink 150.8
[C4 MIM][Cl] [57]
Max-rate Starink 136.6
Starink 97.9
[C6 MIM][Cl] [57]
Max-rate Starink 96.1
Starink 149.7
[C10 MIM][Cl] [57]
Max-rate Starink 139.9
FWO 128.6
Max-rate FWO 149.20
KAS 123.6
[C4 MPy][NTf2 ] [53] Max-rate KAS 144.97
Starink 124.0
Max-rate Starink 144.30

3.2. Arrhenius Methods

According to the data of isothermal TGA, Arrhenius methods directly use Equation (6)
to calculate the values of activation energy and pre-exponential factor. Due to the simplicity
of the calculation process, Arrhenius methods have been used extensively [39,44,71,100,101].
By assuming the decomposition is of zero-order or first-order, the rate constant k( T ) can be
calculated.
For zero-order reactions
k ( T ) = −dm/dt (19)
Equation (19) can be transformed into

E
ln(−dm/dt) = ln( A) − (20)
RT
where m is sample mass, and dm/dt is obtained as the slope of a linear fitting of mass loss
versus time for every isothermal TGA. The activation energy and pre-exponential factor
can be derived from Equation (20). Several studies have applied this method to calculate
the activation energy and pre-exponential factor [47,74,75,78,101]. As shown in Table 5,
Parajó et al. used both the isoconversional methods and the zero-order Arrhenius method
to calculate the activation energies of several imidazolium [NTf2 ] ILs, and they found some
activation energies calculated by the non-isothermal methods are about 20 kJ/mol lower
than those calculated by the isothermal method [44].
Processes 2021, 9, 337 14 of 36

Table 5. Activation energies for the selected ILs by the different methods in the air atmosphere [44].

ILs E/ kJ mol−1
Non-Isothermal Methods Isothermal Method
Zero-Order
Friedman KAS FWO
Arrhenius Method
[C2 MIM][NTf2 ] 102 ± 5 102 ± 7 108 ± 6 122 ± 11
[C3 MIM][NTf2 ] 100 ± 7 92 ± 7 98 ± 7 125 ± 8
[C4 MIM][NTf2 ] 130 ± 6 125 ± 5 130 ± 5 144 ± 8
[C4 MMIM][NTf2 ] 118 ± 11 119 ± 13 124 ± 12 129 ± 5

For the first-order reaction

k( T )·m = −dm/dt (21)

Equation (21) can be transformed into

E
ln(−dm/dt) = ln( A) − + ln(m) (22)
RT
Table 6 shows the values of activation energy and pre-exponential factor calculated by
the first-order Arrhenius method, and these values are quite different from other calculation
results. In the studies of Efimova et al., the activation energy values are calculated using the
isoconversional methods, and then Equation (22) is used to calculate the pre-exponential
factor values [39,71].

Table 6. Activation energy and pre-exponential factor calculated by the first-order Arrhenius method,
zero-order Arrhenius method, and KAS method. Reproduced with permission from Wenlong Wang,
Chemical Engineering Journal; published by Elsevier, 2017; reproduced with permission from Juan
J. Parajó, The Journal of Chemical Thermodynamics; published by Elsevier, 2017; reproduced with
permission from Yuanyuan Cao, Industrial & Engineering Chemistry Research; published by American
Chemical Society, 2014; reproduced with permission from Florian Heym, Chemie Ingenieur Technik;
published by Wiley, 2015.

ILs E/kJ mol−1 A/min−1 Method Reference

[C2 MIM][NTf2 ] 317 7.2 ×1021 First-order Arrhenius method [100]
131.6 1.716 × 1011 Zero-order Arrhenius method [74]
102 - KAS method [44]
[C4 MIM][NTf2 ] 287 7.2 × 1019 First-order Arrhenius method [100]
126.4 3.047 × 1010 Zero-order Arrhenius method [74]
115.9 - KAS method [18]

3.3. Determining the Pre-Exponential Factor

Despite the isoconversional methods are convenient to calculate the values of acti-
vation energy without the reaction model, it is difficult to obtain the values of the pre-
exponential factor. For single-step reactions, the pre-exponential factors can be determined
by the following means when using model-free methods [88].

3.3.1. Using Compensation Effect

Different pairs of the Arrhenius parameters Ak and Ek can be obtained by substituting
different f (α) and experimental data into Equation (8). Although the Arrhenius param-
eters vary widely with f (α), according to the compensation effect, they conform to the
following correlation [88]:
lnAk = aEk + b (23)
Processes 2021, 9, 337 15 of 36

where a and b are the parameters of the compensation effect and are determined by
fitting the pairs of lnAk and Ek at different α into Equation (23). Then for the single-step
reaction, the average pre-exponential factor A0 can be obtained by substituting the average
activation energy E0 determined in non-isothermal experiments into Equation (23). Using
the compensation effect, Haung et al. and Jiang et al. calculated the pre-exponential factors
of [C4 MIM][PF6 ] and [C4 MIM][DBP], respectively [55,56]. The pre-exponential factors of
[C4 MIM][PF6 ] ranged from 9.28 × 103 to 3.89 × 108 min−1 , while those calculated by the
Arrhenius method are 2.6686 × 1011 min−1 [74].

3.3.2. Using Master Plots

Using a non-isothermal TGA, after determining the activation energy values of the
reaction, the reaction mechanism can be simply and accurately determined by plotting
master plots z(α) or y(α) [102,103]. The y(α) function has the following form:
 
E0
y(α) = (dα/dt)α exp = A f (α) (24)
RTα

After determining (dα/dt)α and Tα at different α, it is possible to plot the experimental

values of y(α) against α. Because A is an unknown constant, the shape of the theoretical
master plots y(α) is the same as f (α). The experimental master plots y(α) are normalized
to vary from 0 to 1, then compared with the theoretical shape of f (α) in different kinetic
models in Table 1, and the reaction model of thermal decomposition can be determined.
Finally, A can be easily obtained from Equation (24).
Another function z(α) has the following form:

z(α) = f (α) g(α) (25)

The temperature integral in g(α) can be approximately expressed by the following

formula [97]:
AE
g(α) = exp(− x )[π ( x )/x ] (26)
βR
Eα
x = . (27)
RTα
where
x3 + x2 + 88x + 96
π (x) = (28)
x4 + 20x3 + 120x2 + 240x + 120
Combining Equations (7) and (26) followed by some rearrangement, the following
equation is obtained:
 
2 π (x)
z(α) = f (α) g(α) = (dα/dt)α Tα (29)
βTα
h i h i
π (x) π (x)
where (dα/dt)α Tα2 βTα is an experimental value. It has been proved βTα has a negligi-
ble influence on the shape of experimental master plots z(α) [102,103]. So the correlation
between experimental z(α) and α can be determined from the data of non-isothermal TGA
and DTG. Theoretical master plots z(α) can be drawn according to different kinetic models
in Table 1, and the suitable reaction models can be determined by normalizing experimental
z(α) and the theoretical ones in different kinetic models from 0 to 1 and comparing the
normalized results.
After the reaction model has been established, Williams et al. calculated the pre-
exponential factor values from Equation (24). By comparing the pre-exponential factor
values of [C4 MIM][Cl] calculated by several different methods in Table 7, it can be found
that results calculated by master plots [57] are close to those calculated by the zero-order
Processes 2021, 9, 337 16 of 36

Arrhenius method [74], and those calculated by the first-order Arrhenius method [39] are
much lower.

Table 7. Pre-exponential factor values of [BMIM][Cl] in different investigations. Reproduced with

permission from Anastasia Efimova, The Journal of Physical Chemistry B; published by American
Chemical Society, 2018; reproduced with permission from Michael L.Williams, Thermochimica Acta;
published by Elsevier, 2020; reproduced with permission from Yuanyuan Cao, Industrial & Engineering
Chemistry Research; published by American Chemical Society, 2014.

ln(A)*
ILs
Zero-Order First-Order
Master Plots Method
Arrhenius Method Arrhenius Method
[C4 MIM][Cl] 34.9 [57] 32.2 [74] 20.4 [39]
* A is in min−1 .

4. Influence of Chemical Structure on Thermal Stability

4.1. Influence of Alkyl Chain Length
Processes 2021, 9, x FOR PEER REVIEW 16 of 36
As shown in Figure 11, a method based on the cations exchange of ILs with sodium
montmorillonite clay (MMT−Na+) is adopted to estimate thermal stability from [C2 MIM]+
4.
toInfluence
[C16 MIM] + [104],Structure
of Chemical and theonTThermal Stability
1% and T50% decrease with the increase of alkyl chain length.
4.1. Influence of Alkyl Chain Length
The same conclusion is obtained from quantum chemistry calculation [104]. The thermal
As shown in Figure 11, a method based on the cations exchange of ILs with sodium
stability of 1-alkyl-4-methyl-1,2,4-triazolium iodides shows a small but consistent decrease
montmorillonite clay (MMT－Na+) is adopted to estimate thermal stability from [C2MIM]+
as[Cthe
to chain length is increased from butyl to dodecyl [105]. For the pyrrolidinium [NTf2 ]
16MIM]+ [104], and the T1% and T50% decrease with the increase of alkyl chain length.

ILssame
The in Figure 12,is although
conclusion obtained from Tonset
quantumof [C 8 MPy][NTf
chemistry 2 ] and
calculation [104]. [C
The9 MPy][NTf
thermal 2 ] are higher than
stability of 1-alkyl-4-methyl-1,2,4-triazolium
[C7 MPy][NTf ], it should be stressed iodides
that shows
the a small
longer chain butlength
consistent
has resulted in lower ther-
2
decrease as the chain length is increased from butyl to dodecyl [105]. For the + and [C MPy]+
mal stability on the whole, and the difference
pyrrolidinium [NTf2] ILs in Figure 12, although Tonset of [C8MPy][NTf of T onset between
2] and [C9MPy][NTf23
[C ] MPy] 10
is up
are to 48
higher
◦
thanC[C[72]. Moreover,
7MPy][NTf thebe
2], it should thermal
stressed decomposition
that the longer chain temperatures
length has of [Cn IMBS][HSO4 ]
resulted
generally in lower thermalwith
decrease stability
theonincrease
the whole,ofand the difference
chain length and of Tonset
thebetween
decomposition temperature
[C3MPy]+ and [C10MPy]+ is up to 48 ◦ °C [72]. Moreover, the thermal decomposition
decreases from 311 to 253 C when n increases from
temperatures of [CnIMBS][HSO4] generally decrease with the increase of chain length and
1 to 16. This trend has also been
observed
the in some
decomposition studiesdecreases
temperature of [Cn MIM][Cl] [57],
from 311 to 253 °C[Nwhen ][BScB]from
n increases
8,8,8,n [106],
1 to and [PP1n ][NTf2 ] [107].
16. This trend longer
Generally, has also been observed
the chain in some
length studies of
usually [CnMIM][Cl]
results [57], [N
in lower 8,8,8,n][BScB]
thermal stability, which is proved
[106], and [PP1n][NTf2] [107]. Generally, longer the chain length usually results in lower
by more and more investigations [46,53].
thermal stability, which is proved by more and more investigations [46,53].

467

450
[CnMIM]+
423 425
411
Temperature (℃)

400 396

350

307
300 290
T1%
T50% 266

250
4 6 8 10 12 14 16

Alkyl chain length, n

Figure 11. Thermal stability of MMT–[CnMIM]+ clays at a heating+rate of 10 °C/min in nitrogen
Figure 11. Thermal stability of MMT–[Cn MIM] clays at a heating rate of 10 ◦ C/min in nitrogen
atmosphere [104]. (n = 4,6,10,16)
atmosphere [104]. (n = 4, 6, 10, 16)
Processes
Processes 2021, 9, 337 17 of
of 36
Processes 2021,
2021, 9,
9, xx FOR
FOR PEER
PEER REVIEW
REVIEW 17
17 of 36
36

469
469
470
470

[C MPy]++
[CnnMPy]
460
460

onset (℃) 451

451
450
450 447
447
443
443 443
443
Tonset

440
440
440
440

429
429
430
430

421
421
420
420

22 33 44 55 66 77 88 99 10
10 11
11

Alkyl
Alkyl chain
chain length,
length, nn
12. TTT
Figure 12.
Figure onset
onset
onset ofof
of [Cn[C
[C n MPy][NTf
nMPy][NTf
MPy][NTf 2 ]aaat
22]] at
at a heating
heating
heating rate rate
rate of 10of
of 10 10 ◦ C/min
°C/min
°C/min in in nitrogen
in nitrogen
nitrogen atmosphere
atmosphere
atmosphere [72]. (n[72].
[72]. (n ==
3–10)
3–10)
(n Reproduced
Reproduced
= 3–10) Reproduced with permission
withwith
permission
permission from Gebrekidan
fromfrom
Gebrekidan Gebresilassie
GebrekidanGebresilassie Eshetu,
Eshetu,
Gebresilassie ChemSusChem;
ChemSusChem;
Eshetu, ChemSusChem; pub-
published
published
lished by
by Wiley,
by Wiley, 2017.2017.
Wiley, 2017.

However,
However, there there areare some
some exceptions.
some exceptions. Thermal stability
exceptions. Thermal stability of of 1-alkyl-4-methyl-1,2,4-
1-alkyl-4-methyl-1,2,4-
1-alkyl-4-methyl-1,2,4-
triazolium [NTf
triazolium [NTf22]] ILs
ILs inin Figure
Figure 13 13 reveals
reveals that
thatthere
thereis
there isno
is nocorrelation
no correlationbetween
correlation betweenTTT
between onset and
onset
onset and
alkyl chainlength,
alkyl chain length,and andTTT0.01/10h
and instead
0.01/10hinstead
0.01/10h instead increaseswith
increases
increases withthe
with theincrease
the increaseof
increase ofalkyl
of alkylchain
alkyl chainlength
chain length[75]. [75].
The same
The same
same results
resultsare obtained
results are
are obtained for some
obtained for3,5-dimethylpyrazolum
for some
some 3,5-dimethylpyrazolum
3,5-dimethylpyrazolum ILs and some ILs
ILsparamagnetic
and
and some some
ILs [108,109].
paramagnetic
paramagnetic ILs In the study
ILs [108,109].
[108,109]. In of amino
In the acid
the study
study of ILs, [N
of amino
amino acid
acid ILs,
1,1,14,2O12 ][Lys]
ILs, [N with the
1,1,14,2O12][Lys]
[N1,1,14,2O12 long-chain
][Lys] with
with the alkyl
the long-
long-
group
chain on the
chain alkyl
alkyl side on
group
group of
onnitrogen
the
the side
side ofhas higher thermal
of nitrogen
nitrogen has
has higherstability
higher thermal
thermal than [N1,1,6,2O12
stability
stability than][Lys]
than [N under
[N1,1,6,2O12
1,1,6,2O12 the
][Lys]
][Lys]
isothermal
under
under the condition,
the isothermal while
isothermal condition, both
condition, while longer
while both and shorter
both longer
longer and alkyl
and shorter side
shorter alkyl chains
alkyl side harm
side chains the
chains harm thermal
harm the the
stability
thermal under the
thermal stability
stability non-isothermal
under
under the condition
the non-isothermal
non-isothermal [77].
condition
condition [77].
[77].

194
194 195
195
365
365 365
365

190
190

1-Alkyl-4-methyl-1,2,4-
1-Alkyl-4-methyl-1,2,4- triazolium
triazolium
360
360
185
185
183
183
0.01/10h (℃)
onset (℃)

357
357 180
180
178
178 178
178
T0.01/10h

355
355 177
177
Tonset

355
355
175
175 354
354 175
175

350
350
350
350 170
170

TTonset
onset
164
164 165
165
345
345 346
346 TT0.01/10h
0.01/10h
345
345
160
160
22 33 44 66 88 10
10 12
12

Alkyl
Alkyl chain
chain length,
length, nn
Figure
Figure 13.
13. Thermal
ThermalProperties
Thermal Propertiesof
Properties of1-alkyl-4-methyl-1,2,4-triazolium
of 1-alkyl-4-methyl-1,2,4-triazolium
1-alkyl-4-methyl-1,2,4-triazolium[NTf
[NTf22]] ILs
[NTf 2ILs at
at aat
] ILs a heating
heating rate
rate
a heating of
of 10
rate 10
of
°C/min
◦
°C/min in
in nitrogen
nitrogen atmosphere
atmosphere [75]
[75] (n
(n =
= 1,2,3,5,7,9,11).
1,2,3,5,7,9,11).
10 C/min in nitrogen atmosphere [75] (n = 1, 2, 3, 5, 7, 9, 11).
 Processes 2021, 9, 337 18 of 36

The influence of alkyl chain length on thermal stability can be explained as follows:
(1) Increasing the alkyl chain length weakens the bond between the alkyl chain and the
cation such as imidazolium and ammonium, making it more vulnerable to attack and
therefore more readily thermally decomposed [53,106];
(2) Carbocations and carbon radicals with longer alkyl chains are more stable and easier
to leave on heating, and thus ILs with longer alkyl chains favor the decomposition
phenomenon [72];
(3) For choline based amino acid ILs, longer alkyl chains on cation create strong hy-
drophobic interaction with gradually decreased hydrogen bond interaction due to
bulkier cationic size. Upon decreasing alkyl chain length, the reverse effect renders
lowering the overall thermal stability of the ILs [77].

4.2. Influence of Functionalization and Alkyl Substituents

Comparing the decomposition temperature of some imidazolium ILs and amino
acid ILs with different functional groups in Table 8, the functionalization usually de-
creases the thermal stability of ILs. [C2 MMIM][BF4 ] and [C2 MIM][Br] are more stable than
[C2 NH2 MMIM][BF4 ] and [C2 NH2 MIM][Br] respectively. The reduced thermal stability
is explained by the introduction of amine to the imidazolium cation, which makes the
nearby carbon atom more positively charged and easier to be attacked by the anion [101].
Aromatic functionality also decreases the thermal stability of imidazolium [NTf2 ] ILs, and
the Tonset of IL with two benzyls is higher than that with naphthylmethyl [110].
Hydroxyl functionalization has different effects on the thermal stability of ILs. The decom-
position temperatures of [CnOHMMIM][NTf2] are lower than [CnMMIM][NTf2] (n = 2, 3, 4, 6, 8)
and the maximum difference can reach 48 ◦ C [111]. Similarly, the substitution of the alkyl side
chain to the hydroxyl group in [EMIM][BF4] and [C2MIM][C4F9SO3] reduces their thermal
stability [74,112], which can be attributed to the higher chemical activity and easier decompo-
sition of the hydroxyethyl group [61]. However, Tonset of [C3OHMIM][Cl] (295 ◦ C) [113] are
Processes 2021, 9, x FOR PEER REVIEW
ocesses 2021, 9, x FOR PEER REVIEW much higher than [C3MIM][Cl] (246 ◦ C) [57], and hydroxyl functionalization 19 of 36improves
19 ofalso
36
rocesses 2021, 9, x FOR PEER REVIEW the thermal stability of [EMIM][Ac] and [C2MIM][C4F9CO2] [74,112]. It could 19 be
of 36speculated
cesses 2021, 9, x FOR PEER REVIEW
that the hydrogen bonding interaction between the hydroxyethyl group and anion
19 of 36
results in
this trend, and the higher intramolecular hydrogen bond interaction stabilizes
Table 8. Thermal stability of ILs with different functional groups at a heating rate of 10 °C/min in ILs and block
Table 8. Thermal stability of ILs with different functional groups at a heating rate of 10 °C/min in
an inert
Table thermal
atmosphere.
8. Thermal decomposition reaction to some extent [74].
stability of ILs with different functional groups at a heating rate of 10 °C/min in
an inert atmosphere.
an inert atmosphere.
Table 8. Thermal ILs Structure
stability of ILs with different of Cations
functional groups at agroupsTatonset
heating rate /°C Reference
of 10 °C/min in ◦ C/min in an
ILs 8. Thermal stability ofStructure
Table ILs with different functional
of Cations Tonseta/°C
heating rate of 10
Reference
an inert atmosphere.
ILs Structure of Cations Tonset/°C Reference
inert atmosphere.
ILs Structure of Cations Tonset/°C Reference
ILs 4]
[C2NH2MMIM][BF Structure of Cations /◦ C
Tonset284 [101]Reference
[C2NH2MMIM][BF4] 284 [101]
[C2NH2MMIM][BF4] 284 [101]
[C2NH2MMIM][BF 4]
[C2 NH2 MMIM][BF4] 284
284 [101] [101]

[C2MMIM][BF4] 391 [101]

[C2MMIM][BF4] 391 [101]
[C2MMIM][BF 4]
[C2 MMIM][BF4] 391
391 [101] [101]
[C2MMIM][BF4] 391 [101]

[C2NH2[C
MIM][Br]
2 NH2 MIM][Br] 222
222 [113]
[C2NH2MIM][Br] 222 [113] [113]
[C2NH2MIM][Br] 222 [113]
[C2NH2MIM][Br] 222 [113]
[C2 MIM][Br] 300 [71]
[C2MIM][Br] 300 [71]
[C2MIM][Br] 300 [71]
[C2MIM][Br] 300 [71]
[C 2MIM][Br]
[C7MIM][NTf2]
300437 [71]
[110]
[C7MIM][NTf2] 437 [110]
[C7MIM][NTf2] 437 [110]
[C[BnzMIM][NTf
7MIM][NTf2] 2]
[BnzMIM][NTf 2]
437421
421
[110]
[110]
[110]
[BnzMIM][NTf2] 421 [110]
[BnzMIM][NTf2] 421 [110]
[(Bnz)2IM][NTf2] 410 [110]
Processes 2021, 9, x FOR PEER REVIEW
[C2MMIM][BF4] 391 [101] 19 of 36
[C MMIM][BF
[C22MMIM][BF 4]
2MMIM][BF4]
391
391 [101]
[101]
[C 4] 391 [101]

Table 8. Thermal stability of ILs with different functional groups at a heating rate of 10 °C/min in
Processes 2021, 9, 337 an inert atmosphere. 19 of 36
[C [C
NH2NH2MIM][Br]
2MIM][Br] 222222 [113]
[113]
[C22NH
[C 2NH2MIM][Br]
2MIM][Br] ILs
222
Structure of Cations 222 [113]
[113]
Tonset/°C Reference

Table 8. Cont.
[C [C2MIM][Br]
MIM][Br] 300300 [71]
[71]
[C22MIM][Br]
[C 2MIM][Br]
[C2NHILs
2MMIM][BF4]
Structure of Cations 300
300
Tonset /◦ C 284[71] Reference
[71] [101]

[C [C7MIM][NTf
MIM][NTf 2]
2]
[C7 MIM][NTf2] 437437
437 [110] [110]
[110]
[C77MIM][NTf
[C 7MIM][NTf2]
2]
437
437 [110]
[110]
[BnzMIM][NTf
[BnzMIM][NTf 2]
2]
[BnzMIM][NTf 2] 421
421 421 [110]
[110]
[BnzMIM][NTf
[BnzMIM][NTf 2]
2]
[C2MMIM][BF 4]
421
421 [110] [110]
[110]
391 [101]

[(Bnz)
[(Bnz) 2IM][NTf2]
IM][NTf ] 410 410 [110]
[110]
[(Bnz)22IM][NTf
[(Bnz) [(Bnz)222IM][NTf
2IM][NTf
]2] 2] 410
410
410 [110] [110]
[110]

[C2NH2MIM][Br]
[NapmMIM][NTf 2] 406 222 [110] [113]
[NapmMIM][NTf
[NapmMIM][NTf 2]
2]
406
406 [110]
[110] [110]
[NapmMIM][NTf 2]
[NapmMIM][NTf 2] 406
406 [110]
-
[NTf[NTf
2 - ]-
[NTf ]- 2]
2MIM][Br]
[C[NTf2] N+ + N
2 + 300 [71]
Moreover, NN + ether in alkyl side chains is favorable for thermal decomposition. As the

400400
400 number
400 385 385of introduced ether
[NTf - 2increases,
[NTf ]- the thermal stability tends to decrease [66,114–116]
385 2]- ]-
[NTf
380 385
because the introduction [NTf 2
2] of
N + N+
oxygen atoms weakens the interaction437 between the cation
380
380 [C 7 MIM][NTf 2 ] OO O
NN +
+ [110]
380 and anion [77,115]. OSpecifically, Figure 14
- 2]demonstrates that the oxygen atom at the
-
[NTf
360360 349 348
[NTf 2]- ]-
[NTf +
360 β-position significantly
360 349
349 decreases
348
348 the [NTf2] N+ + N stability of ILs, which can be explained
O thermal
2
349 N
T10% (℃)

[BnzMIM][NTf 2] 348 O N + 421 [110]

(℃)

340by retro-alkylation of piperidinium O

ILs into 1-methyl piperidine and the corresponding
10%(℃)

340 O
(℃)

340
340
320oxocarbenium - ion
- intermediates at elevated temperature [117]. In addition, the length of the
[NTf [NTf 2] 314 [NTf
- 2]
-
320 2] ]- 314 [NTf
320 O[NTf - + N+
2 314 [NTf2] ]- +
320 O-alkylO [NTf
chain 2 ] Nalso influences thermal314 stability. However, O
- +itNis
2 interesting that the increase
10%

O N + [NTf
OO 2] NN+
10%

+
300 [(Bnz)
O 2 IM][NTf
N 2 ] O N + 410 [110]
300
300 of the length of the oxygen alkyl chain improves the thermal stability in isothermal TGA,
TTT

300
280280while the conclusion obtained by non-isothermal - 268
TGA is opposite
O
O [77]. This contradiction
280 between the results of non-isothermal
280 [NTf [NTf
- 2]
2] ]- TGA 268268and isothermal O
TGA
O O
has
O
also been[110]
found in
[NapmMIM][NTf ] [NTf
[NTf ]2-
ON+ N +
268 259 259 O
O 406
260260 2
OO O OO NN
O 2 + 259
259 253 253
260
260
other studies [44,57,75,78,110]. +
253
253
O
240240
240
240 [PP16][NTf2] [PP1EP][NTf 2] 2][PP
- 1PE][NTf2] [PP1MB][NTf2] [PP1MEM][NTf2] [PP1BM][NTf2] [PP1MEEM][NTf2]
[PP16][NTf 2] [PP1EP][NTf2] [NTf
[PP 1PE][NTf2] [PP1MB][NTf2] [PP1MEM][NTf2] [PP1BM][NTf2] [PP1MEEM][NTf2]
[PP ][NTf2] [PP1EP][NTf2] [PP1PE][NTf
+ 2] [PP1MB][NTf2] [PP1MEM][NTf2] [PP1BM][NTf2] [PP1MEEM][NTf2]
[PP1616
][NTf2] [PP1EP][NTf2] [PP1PEN
][NTf2] [PP1MB][NTf2] [PP1MEM][NTf2] [PP1BM][NTf2] [PP1MEEM][NTf2]

ILs
ILs - ILs
400
385
ILs
[NTf2]
Figure
Figure 14. 14. Thermal
Thermal stability
stability of piperidinium
ofofpiperidinium ILs ILs
withwith
Nan
an oxygen
+ oxygen atom-containing
atom-containing alkyl
alkyl sideside chain
chain
Figure
Figure 14.
14. Thermal380
Thermal stability
stability piperidinium
of piperidinium ILs
O with
ILs with anoxygen
an oxygenatom-containing
atom-containingalkyl
alkylside
sidechain
chain
at a heating
at aaheating rate
rate of
ofof10 10 °C/min
°C/min in argon
ininargon atmosphere
atmosphere [117].
[117]. Reproduced
Reproduced with permission from T. T.
with permission from
atataNokami,
heatingrate
heating rateof
360
Faraday 1010°C/min
°C/minin
Discussions;
argonatmosphere
argon atmosphere[117].
published by Royal
[117].Reproduced
Reproduced
Society of
- with permission from T.
[NTf2]with
Chemistry, permission from T.
2018.
Nokami, Faraday
Nokami,Faraday Discussions;
FaradayDiscussions; published
Discussions;published
published349by Royal
byRoyal
Royal Society
348 ofofChemistry,
Societyof Chemistry, N2018.
+
2018.
Nokami, by Society Chemistry,
O 2018.
T10% (℃)

340
320 [NTf2]- 314 [NTf2]-
O N+ O N+
300
280 268
O
[NTf2]- O
O N+ 259
260 O 253

240
[PP16][NTf2] [PP1EP][NTf2] [PP1PE][NTf2] [PP1MB][NTf2] [PP1MEM][NTf2] [PP1BM][NTf2] [PP1MEEM][NTf2]

ILs
Figure14.
Figure Thermalstability
14.Thermal stability of
of piperidinium
piperidinium ILs with an oxygen atom-containing
atom-containing alkyl
alkyl side
side chain
chain at
a heating
at rate
a heating of of
rate ◦ C/min
10 10 °C/min ininargon atmosphere
argon atmosphere[117]. Reproduced
[117]. Reproducedwith permission
with from
permission T. Nokami,
from T.
Nokami, Faraday Discussions;
Faraday Discussions; published published
by Royal by RoyalofSociety
Society of Chemistry,
Chemistry, 2018. 2018.

In addition to functional groups, the alkyl substituents also affect thermal stability.
Ngo et al. [118] found that the thermal stability of the imidazolium ILs is improved by
increasing the degree of substitution of hydrogen by alkyl groups on the imidazolium
ring, the potential energy barrier for an attack is increased. Methyl substitution in C2
(the carbon atom between two nitrogen atoms in the imidazolium ring) enhances the
 Processes2021,
Processes 2021,9,9,xxFOR
FORPEER
PEERREVIEW
REVIEW 2020ofof36
36
Processes 2021,
Processes2021,
2021,9,9,9,xxFOR PEER
FORPEER REVIEW
PEERREVIEW
REVIEW 20 ofof36
20of 36
Processes
Processes2021, x
2021,9,9,x xFORFOR
FORPEER
PEERREVIEW
REVIEW 20 36
rocesses
rocesses 2021,9,9, 2020ofof3636
ocesses 2021, x xFOR
FORPEER
PEERREVIEW
REVIEW 2020ofof3636

InInaddition
additiontotofunctional functionalgroups, groups,the thealkyl alkylsubstituents
substituentsalso alsoaffectaffectthermalthermalstability. stability.
In
In addition
addition toto functional
functional groups,
groups, the
the alkyl
alkyl substituents
substituents also
also affect
affect thermal
thermal stability.
stability.
Processes 2021, 9, 337 Ngo
Ngo InIn et al.
addition
etaddition [118]
al. [118]
[118] toto found
foundfunctional
functional that the
that groups,
the groups,
groups, thermal
thermal the stability
thestability
alkylsubstituents
alkyl of
of the the
substituents imidazolium
the imidazolium alsoaffect
imidazolium
also affectILs ILs
thermalis improved
is improved
thermal stability.
improved
stability. by20 of 36
by
NgoIn
In
Ngo etet al.
addition
additional. to
to
[118] found
functional
functional
found that
that the
groups,
the thermal
thermalthe
the stability
alkyl
alkyl
stability of
substituents
substituents
of the also
also
imidazolium affect
affect ILs
thermal
thermal
ILs isis stability.
stability.
improved by
by
In
Ngo addition
increasing
etal.
increasing
Ngo al.[118]
[118]
theto found
the functional
degree
found
degree that groups,
ofofthesubstitution
thethermal
substitutionthermal the of alkyl
of
stabilitysubstituents
hydrogen
hydrogen ofthethe
by alsogroups
byimidazolium
alkyl
imidazolium
alkyl affect
groupsthermal onis
ILs
on the
is
the stability.
imidazolium
improved
imidazolium by
Ngo
Ngo
Ngo etet
increasing
et al.[118]
al.
increasing
et al. [118]
[118] the
the degree
found
found
found degree
that
that
that
that
of
of
the
substitution
the
the thermalstability
thermal
substitution
thermal
ofstability
hydrogen
stability
stability
ofhydrogen
hydrogenofofof
of theby
the
the
alkyl
imidazolium
imidazolium
by groups
alkylgroups
imidazolium groups ILs
ILs
ILs
ILs onon
isis the improved
isimproved imidazolium
improved
improved
the imidazolium by by
by
by
ring,
increasing
ring, the
increasing the
thethe potential
the
potential
thedegreedegree
degree energy
energy of barrier
substitution
barrier for for
forofan an
of attack
anhydrogen
attack is is increased.
by
is increased.
increased. alkyl Methyl
Methylon substitution
on the
substitution in
imidazolium
in C C 2 (the
C22 (the
(the
ring,
increasing
increasing
ring, the potential
the degree
potential ofof
energy
of
energy
substitution
barrier
substitution
substitution
barrier for
of
ofan
hydrogen
attack
hydrogen
an attack isbyby
by
byalkylalkylgroups
alkylgroups
increased.
groups
Methyl
groups
Methyl on
on
the
theimidazolium
substitution
the imidazolium
imidazolium
substitution in
increasing
carbon
ring,
carbon
ring, the
the theatom
atom degree
potential
potential between
between of
energy
energy substitution
two
two nitrogen
barrier
nitrogen
barrier forforofan hydrogen
atoms
atoms attack
attack in inis the
is
the alkyl
imidazolium
increased.
imidazolium
increased. Methyl
Methyl ring)on
ring) the
substitution
enhances
substitution imidazolium
enhances the
ininin
the C
C 2 (the
Cthermal
2 (the
thermal
(the
carbon
ring,
ring, the atom
thermal
thepotential
potential
potential between
stability
energybarrier
energy two nitrogen
[45,74,119].
barrier
barrier foran
for anatoms
an C-2H
attack
attack in
acidity the imidazolium
isincreased.
is of
increased.
increased. the imidazolium
Methyl
Methyl ring) enhances
ring is one
substitution
substitution the
in
in Cof22thermal
2
the structural
(the
ring, carbon
the
stability
carbon
stability
carbon
atom
atom
atom
between
energy
[45,74,119].
between
[45,74,119].
between two
C－2H
two
two
C－2H nitrogen
for
acidity
nitrogen
acidity
nitrogen
atoms
attack
of
atoms
of
atoms thein
the isin
in the
imidazolium
the
imidazolium
the
imidazolium
imidazolium
imidazolium Methyl
ring
ring isis
ring)
ring)
one
ring) of
enhances
substitution
one of thestructural
enhances
the
enhances in
structural
the CC
the
the (the
thermal
(thefactors
2 thermal
factors
thermal
stability
carbon
carbon atom
atom
stability [45,74,119].
factors
between
between determining
[45,74,119]. C－2H
two
two C－2H acidity
short-term
nitrogen
nitrogenacidity atomsof
atoms of the
thein imidazolium
thermal
in the
the stability
imidazolium
imidazolium
imidazolium ring
ring is
because
ring)
ring)
is one
one of
the
enhances
enhances
of the
most
the structural
acidic
the
the
structural thermal
thermal factors
proton
factors on the
carbon atom
determining
stability
determining
stability between
[45,74,119].
[45,74,119]. two
short-term
short-term nitrogen
C－2Hacidity
C－2H thermal
acidity
thermal atoms
of in
stability
ofstability the
theimidazolium
the imidazolium
imidazolium becausering
because ring
the ring)
theisismost
most enhances
acidic
oneofofacidic
one the
thestructural
the structural
proton thermal
protonfactors on the
factors
on the
determining
stability
stability imidazolium
[45,74,119].
[45,74,119]. short-term
C－2H
C－2H cation thermal
locates
acidity
acidity of
of atstability
the
the C [58].
imidazolium
2imidazolium because ring
ring theis most
one
isone
one of acidic
the proton
structural on
factors the
determining
stability [45,74,119].
imidazolium
determining
imidazolium
determining
short-term
C－2H
cation
short-term
cation
short-term locates
locates
thermal
acidityatat
thermal
thermal CCof 2 the
[58].
2 [58].
stability
imidazolium
stability
stability
because
because
because ring the
is
the
the most
most ofofthe
most the
acidic
acidic
structural
acidic
structural proton
proton
proton
factors
factors
on onon the the
the atom
imidazolium
determining
determining
imidazolium Moreover,
cation
short-term
short-term
cation locatesTable
thermal
thermal
locates atat9C Cshows
2 [58].
stability
stability
[58]. the because
bonding
because of
the
the the alkylacidic
most
most chain
acidic via
proton
proton tertiary on
on carbon
the
the
determining
imidazolium
Moreover, short-term
Moreover, cation Table
Table thermal
locates 9shows
shows
atat stability
2thebonding
[58].
C2 2[58]. bonding because ofofcompared
the the alkylmost chain acidic proton carbon
viatertiary
tertiary on theatom
carbon atom
imidazolium
imidazolium
imidazolium decreases
Moreover,
Moreover,
cation
cation
cation the
Tablelocates
locates
locates
Table 999 shows
thermal at
at C
C
shows
C the
2stability
the
[58].
[58]. thethe of the IL,
bonding
bonding of
ofthe
the
the alkyl
alkyl
thealkylalkyl
chain
to
chain
chainthose via
via
via isomers,
tertiary
tertiary in whichatom
carbon
carbon the alkyl is
atom
imidazolium
decreases
Moreover,
decreases
Moreover, cation
the
theTable locates
thermal
Table
thermal
Table 9 at C
shows
stability
9shows
shows 2 2[58].
stability the of
the
ofbonding
the IL,
bonding compared
IL, compared
bonding compared of toto those
those chain isomers,
via
isomers, in
tertiary
in which
which carbon the
theatom alkyl
atom
alkyl isis
decreases
Moreover,
Moreover,
decreases
Moreover,
connected
the
the thermal
Table
thermal
Table
with
9
the
shows
shows
secondary
stability
99secondary
stability the
the
the
ofof the
bonding carbon
IL,
theIL,
bonding IL, of ofof
of atom
compared the
the
the
thealkyl alkyl
to
alkyl
alkyl
tothe
to thosechain
imidazolium
chain
chain
those
chain via
viatertiary
isomers,
via
isomers,
via
tertiary
tertiary
tertiary
ring
in which
inwhich
carbon
[66,120].
carbon
carbon
which
carbon
the
the
atom
atom
atom
The potential
alkyl
alkyl is
is
connected
decreases
connected
decreases the
the with
with thermal
thermal the
the secondary stability
secondary
stability ofcarbon
carbonthe atom
atom compared to
to the the
theto imidazolium
to those
imidazolium isomers, ring [66,120].
in
ringin[66,120].
[66,120]. The
Thethe potential
alkyl
potential is
connected
decreases
decreases
connected
decreases
energy
thethe
the with
with
thermal
barrier
thermal
thermal the
the stability
stability
secondary
stability of ofof
of the decomposition
of the
the
theIL,
carbon
the
carbon IL,
IL,
IL,atom
compared
compared
compared
atom
compared
reaction
toto theto to
to thoseisomers,
decreases
imidazolium
those
those
imidazolium
those
isomers,
because
isomers,
isomers,
ring
ring
in in
inthewhich
which
which
[66,120].
which the
the
thealkyl
decomposition
The
theThe
alkylisisproducts
potential
alkyl
alkyl is
potential
is
energy barrier
connected
energy
connected barrier
withthe
with the of
of the decomposition
secondary
the
secondary decomposition
carbon
carbon atom
atom reaction
toto
reaction the
the decreases because
imidazolium
decreases
imidazolium because
ring
ring [66,120].
[66,120]. the The
the decomposition
Thepotential
potential
decomposition
energy
connected
connected
energy originating
barrier
with
with
barrierthe ofoffrom
thesecondary the
secondary
secondarythe tertiary
decomposition
carbon
carbon
decomposition carbonatom
atom can
to be
reaction
to the
the
reaction easily
imidazolium
imidazolium stabilized
decreases
decreases ring
ring [66,72].
because[66,120].
[66,120].
because the
the decomposition
The
The potential
potential
decomposition
connected
products
energy
products
energy with
barrierthe
originating
originating
barrier of the from
from carbon
tertiary
decomposition
tertiary carbonatom carbon
carbon to the
reactioncan
can beimidazolium
bebe easily
decreases
easily stabilizedring
stabilized [66,120].
because
stabilized [66,72].
[66,72].the The potential
decomposition
products
energy
energy
energyproductsbarrier
barrier
barrier ofof
originating
of
originating
of the
the
the
thefrom decomposition
tertiary
decomposition
decomposition
fromtertiary
decomposition tertiarycarbon
reaction
reaction
reaction
carbon
reaction
can
canbe
decreases
easily
decreases
decreases
beeasily
decreases
because
because
because
easilystabilized
stabilized
because the
thedecomposition
[66,72].
the
[66,72].
the
decomposition
decomposition
decomposition
products
products originating
originating
Table 9. T of from
from tertiary
several isomeric carbon and can
can be
quasi-isomericeasily stabilized
ILs at a [66,72].
[66,72].
heating rate of 10 ◦ C/min in argon
products
products originating 5% from tertiary carbon canbe beeasily
easily stabilized [66,72].
products
Table
Table 9.originating
Tableoriginating
9.TT5%5%ofofseveral
several
atmosphere [66].
9.9.TT5%5%of several
from
from
isomeric and
tertiary
isomeric
tertiary
isomeric and
quasi-isomeric
and carbon
carbon
ILs
can
quasi-isomeric
can
quasi-isomeric
atataaheating rate
be
of 10
easily
ILsatat
ILs
°C/min
stabilized
aheating
heatingrate
stabilized
a
ininargon
[66,72].
rate
[66,72].
ofof10 10°C/min
°C/minininargon argon
Table
atmosphere
Table 9.T T 5% of
of severalisomeric
[66].
several isomericand
andquasi-isomeric
quasi-isomericILsILsat heatingrate
aheating
heating rateofof10
10°C/min
°C/minin argon
argon
atmosphere
Table 9.
atmosphere [66].
5% of[66].
several isomeric and quasi-isomeric ILs at a rate of 10 °C/min in argon
Table
Table 9. T
T5%
atmosphere
9. of several
5% of several
[66]. isomeric and
isomeric and quasi-isomeric
quasi-isomeric ILs
ILs at
at aa heating
heating rate
rate of
of 10
10 °C/min
°C/min in
in argon
argon
atmosphere
Table [66]. isomeric
9. T5% of [66].
several and quasi-isomeric Structure
ILs at a heating rate of 10 °C/min in argon T5% /◦TC5%/°C
atmosphere
atmosphere
atmosphere
atmosphere
[66]. ILs
[66].
[66].
ILs ILs Structure
Structure
of Cations
ofCations
of Cations T5%5%/°C
ILs ILs Structure of Cations T /°C
StructureofofCations
Cations T 5%/°C
ILs
ILs Structure
Structure ofCations
Cations T T5%5%/°C
/°C
ILs
ILs
[ethoxyC
ILs 55IM][NTf5IM][NTf
[ethoxyC 5 IM][NTf2] 2]
Structure
Structure of
of Cations
Structure of Cations T
T
377.3
T5%/°C
5% /°C
5%/°C
377.3
[ethoxyC
[ethoxyC IM][NTf 2]
2]
377.3
377.3
[ethoxyC
[ethoxyC5IM][NTf 5IM][NTf2]
5IM][NTf2]
377.3
377.3
[ethoxyC
[ethoxyC IM][NTf 2]
2] 377.3
377.3
[ethoxyC
[ethoxyC 55IM][NTf
5IM][NTf 2]2] 377.3
377.3
[ethoxyiC
[ethoxyiC 5IM][NTf
5IM][NTf
[ethoxyiC 2]
5 IM][NTf
2]
2] 372.7 372.7
372.7
[ethoxyiC
[ethoxyiC 5IM][NTf
5IM][NTf2]
2] 372.7
372.7
[ethoxyiC
[ethoxyiC 5IM][NTf2]
5IM][NTf2]
372.7
372.7
[ethoxyiC
[ethoxyiC
[ethoxyiC IM][NTf
55IM][NTf
5IM][NTf
2]
2]2]
372.7
372.7
372.7
[ethoxyneoC
[ethoxyneoC 5IM][NTf2]
5IM][NTf2]
369.8
369.8
[ethoxyneoC[ethoxyneoC
[ethoxyneoC 5IM][NTf
5IM][NTf
2]
5 IM][NTf
2] 2] 369.8369.8
369.8
[ethoxyneoC
[ethoxyneoC 5IM][NTf2]
5IM][NTf2]
369.8
369.8
[ethoxyneoC
[ethoxyneoC5IM][NTf
[ethoxyneoC 5 IM][NTf
5IM][NTf 2]2]
2 ] 369.8
369.8
369.8
[ethoxycC5IM][NTf
[ethoxycC 5IM][NTf2]
2]
355.4
355.4
[ethoxycC
[ethoxycC 5IM][NTf2]
5IM][NTf
[ethoxycC 2]
355.4
355.4
[ethoxycC 5IM][NTf 5 IM][NTf
2] 2] 355.4
355.4
[ethoxycC
[ethoxycC 5IM][NTf2]
IM][NTf 2]]
355.4
355.4
[ethoxycC 5IM][NTf
[ethoxycC5IM][NTf2]
5 2 355.4
355.4
[ethoxy3C5IM][NTf
[ethoxy3C 5IM][NTf2]
2]
354.3
354.3
[ethoxy3C
[ethoxy3C 5IM][NTf2]
5IM][NTf2]
354.3
354.3
[ethoxy3C
[ethoxy3C 5IM][NTf
[ethoxy3C
5IM][NTf2]5 2]
IM][NTf2] 354.3
354.3
354.3
[ethoxy3C
[ethoxy3C
[ethoxy3C IM][NTf
55IM][NTf
5IM][NTf
2]
2]2]
354.3
354.3
354.3

[C[C4C 4C5IM][NTf2]
5IM][NTf2]
413.2
413.2
[C[C 4C5IM][NTf2]
4C5IM][NTf2]
413.2
413.2
[C [C 4C5IM][NTf2]
4C5IM][NTf 2]
[C4 C25]IM][NTf 413.2
413.2
[C C IM][NTf 2] 413.2
413.2
[C[C4C 44C 55IM][NTf
5IM][NTf 2]2] 413.2
413.2
[C [C4iC 4iC5IM][NTf2]
5IM][NTf2]
402.3
402.3
[C[C 4iC5IM][NTf2]
4iC5IM][NTf2]
402.3
402.3
[C [C4iC 4iC5IM][NTf2]
5IM][NTf2]
402.3
402.3
[C[C
[C4iC
iC
44iC IM][NTf
55IM][NTf
5IM][NTf
[C4 iC225]]IM][NTf2 ]
2]
402.3
402.3
402.3
402.3
[C
[C44cC 4cC5IM][NTf2]
cC55IM][NTf
IM][NTf22]] 365.9
365.9
[C[C 4cC5IM][NTf2]
365.9
365.9
[C[C 4cC5IM][NTf2]
4cC5IM][NTf2]
365.9
365.9
[C[C
[C4cC
cC
44cC IM][NTf
55IM][NTf
5IM][NTf [C4 cC 2]
2]25]IM][NTf2 ]
365.9
365.9
365.9
365.9

[C43C
[C 43C5IM][NTf2]
5IM][NTf2]
362.9
362.9
[C
[C43C5IM][NTf2]
43C5IM][NTf2]
362.9
362.9
[C
[C 43C5IM][NTf2]
43C5IM][NTf2]
362.9
362.9
[C
[C
[C43C
3C
443C IM][NTf
55IM][NTf
5IM][NTf
2]
2]25]IM][NTf2 ]
[C4 3C
362.9
362.9
362.9
362.9

4.3.Influence
4.3. InfluenceofofAnions Anionsand andCations
Cations
4.3. Influence
4.3.Influence
Influenceof ofofAnions
Anionsand and Cations
andCations
Cations
4.3.
4.3.Influence
InfluenceAnions ofAnions Anions
playaamajor
Anions major
andCations roleinindetermining
Cations determiningthermal thermalstability, stability,which whichhas hasbeen beenconfirmed
confirmed
4.3.
4.3. Influence Anions
Anions of play
ofAnions
play
Anions aaand and
major
and role
role
Cations in determining thermal stability, which has been confirmed
4.3. Influence
in manyAnions
Anions of studies
play
4.3.studies play
Influence a major
major Cations
[46,58,59].
of Anions role
role For
in
andin determining
1,2,4-triazolium
determining
Cations thermal thermal
thermal ILs, stability,
the
stability, stability which
which has
increases
has been
been in confirmed
theorder
confirmed order
inAnions
in many
Anions
many playa amajor
－ studies
play [46,58,59].
major
[46,58,59]. roleinFor
role For
in 1,2,4-triazolium
determining
－ 1,2,4-triazolium
determining thermal ILs,
ILs, the stability
stability,
－ the
stability, stability whichincreases
which increases
hashasbeen in
beenconfirmed
in the
confirmed
the order
in Anions
Anions
[NTf many play
studies
play
2] studies> Anionsa
[OTf]a major
major － role
[46,58,59].
role inin determining
For
determining1,2,4-triazolium － thermal
thermal stability,
ILs,
stability, the which
stability
－
which hashas been
increases
been － confirmed
in
confirmed the order
in
inin [NTf
many
[NTf
many
many －
2] －－studies
2]－studies>>> [OTf]
[OTf] －
[46,58,59].
－ play
[46,58,59].－ > >> [OTs]
[46,58,59]. [OTs]
[OTs]
aFor For
For
major
－ > [BF
>>>role
[BF
1,2,4-triazolium
－ 1,2,4-triazolium
[BF
1,2,4-triazolium
－ in 4]－
4] －－ > [OMs]
4]－determining
> [OMs]
>> [OMs]
ILs,
ILs,
ILs,
－
－the
the
－
the
thermal>stability
[I]－ stability,
stability
>>>stability
[I]
[I]
stability
－
－ > >>increases
[NO
[NO increases
increases
[NO
3]
－
3] －－ (Table
3]which
(Table
inin
(Table
in hasthe
the
the 10).
10).
been order
order
10).
order ForFor
confirmed
For
inin many
[NTf
many
[NTf ]
－2]studies
studies
tributyltetradecyl
tributyltetradecyl
2
] in > [OTf]
[OTf]
many
[46,58,59].
[46,58,59].
－
－
> >[OTs]
phosphonium
studies
For
[OTs]
For
phosphonium － 1,2,4-triazolium
－ 1,2,4-triazolium
[46,58,59]. > [BF
ILs,
[BF
ILs, 4 ]
－4]
the > ILs,
[OMs]
ILs,
stability
[OMs]
]the>1,2,4-triazolium
stability － the
－
the >
increases
[I]
stability
increases [I] －
－ in>the
in the
increases
>increases
[NO
[NO order
order 3 ]
－ ] [PFOS]
3－ inin
(Table
[PFOS]
the
(Table
the >order
-order
>10).
10).
[NPf
10).
[NPf For
2]
For
2-]- >
> order
]－For ILs, >the stability increases in the
-
[NTf
[NTf －
tributyltetradecyl
2－ >[OTf]
[OTf] － >[OTs]
[OTs]
>－phosphonium － > [BF ILs, －
－the
4－ >stability
[OMs] － >[I][I]
－－increases
－
in the [NO order]3－] (Table
－ (Table
[PFOS] ->
- >[NPf
For 2]- ->
[NTf
[NTf ]22]－] 2>]2－－]>>[NTf
tributyltetradecyl
2[NTf
tributyltetradecyl
[NTf
tributyltetradecyl
－ [OTf]
[OTf]
>>[FeCl
[FeCl
]
－－
− 4> 4>
] ]>phosphonium
－
>
[OTf]
[OTs]
phosphonium
[OTs]
>[AOT]
phosphonium
－ [AOT]
－－ －> [BF
>>>[BF
− >－－[OTs] [BF
>[OS]
[OS]
ILs,
ILs, − ]44－]>
4ILs,
－
the
the
the
>(Table
(Table
[BF
[OMs]
>stability
[OMs]
stability
[OMs]
]
stability >11).
− 11). For
[OMs] >>>nitrile-functionalized
For
increases
increases
[I]－－ >in
increases
[I] >>in
−[NO
nitrile-functionalized
− > [I]
in the
[NO
[NO
the>
theorder
[NO
order
33]
3]order
－
]
(Table
(Table
[PFOS]
[PFOS]
−
[PFOS]
10).
-10).
-10).
azepanium
azepanium
(Table > >10).[NPf
[NPf
For
For
[NPf
For For]
]> >
]2>-ILs,
2-ILs, tributyl-
[NTf
tributyltetradecyl
tributyltetradecyl2]－ > [FeCl4phosphonium
－ 2 ]4－] >>[AOT]
－
phosphonium － >>
－ [OS]
ILs,
ILs, － (Table
the
the － 4
stability
stability 11). For－ nitrile-functionalized
increases
increases inthe theorder order 3
[PFOS] －azepanium
- >[NPf
[NPf ]>- >>ILs,
2
-
[NTf
tributyltetradecyl
[NTf
the
[NTf ]2]>tetradecyl
the2－－stability
]2－stability
>[FeCl
>[FeCl[FeCl phosphonium
increases
]4－]> >[AOT]
increases
－ >[AOT][AOT]
inin
[AOT]
phosphonium the
－
the
－ >ILs,
order
order
>order
[OS]
[OS]
[OS] the
－
－ILs, [OTf]
[OTf]
(Table
(Table
the
(Table
－
－ >
－
stability 11).
>11).
11).
stability
[PTS]
For
increases
[PTS] For
For
－ >[CH
[CH inin the
nitrile-functionalized
3SO
>nitrile-functionalized
increases 3SO4in
－ nitrile-functionalized
order
－
]4－－] the
>>[OMs]
[PFOS]
[PFOS]
[OMs]
order
->
>>[Br]
－ azepanium
－ [PFOS]
[Br]
azepanium
[NPf
-azepanium
[Br] － −
－ 22-]
－ 2]> [TFA]ILs,
ILs,
>ILs,
>ILs,
[TFA] [NPf2 ]− >
[NTf
[NTfthe ] stability
2](Table > [FeCl increases
] 4－ in－－ the > [OS] －－ [OTf] (Table >
－ 11). [PTS]
For －> [CH 3SO4]－ － > [OMs]
nitrile-functionalized －>
azepanium －> [TFA]
[NTf the
－ －
2
－2]stability
the
－ >>[FeCl
stability [FeCl
stability 12
4－
]−>For
4increases > [AOT]
]4)increases
>[AOT]
inthe
choline
inin
the
− >[OS]
[OS]
>basedorder(Table
based
order (Table
[OTf]
amino
[OTf] −－ － －
>11).
11).
acid >[PTS]For
[PTS]
For
ILs,
− － nitrile-functionalized
>[CH
[CH 3SO
－nitrile-functionalized
>the
>[CH stability
3SO
4] >[OMs]
increases
]4－]increases
>[OMs][OMs] azepanium
－
azepanium
－ in>the >[Br]
>the [Br] －
order
－ >ILs,
>ILs, [TFA]
[Tau]
[TFA] －
－
the
the (Table
(Table
stability
－
[NTf12
12 2)] For
increases
)
increases For [FeCl
choline
choline
in the 4 ] order
the >
order
based [AOT] amino
[OTf]
amino
[OTf] －－ >
>acid
>[OS]
acid [PTS]
[PTS] －(Table
ILs,
ILs,
－－ >
the
the[CH 11). 3SOFor
stability
stability
SO ] －
4－
> nitrile-functionalized
increases
>[OMs] － in
－－ in > [Br]
the
[Br] －－
order
－
order> >[TFA] azepanium
[Tau]
[TFA]
[Tau] －
－
the－ stability
(Table 12the )For
increases For inthetheorder
incholine order
based [OTf]amino >acid
[PTS]
acid ILs, >[CH[CH
the 3SO 4]4] >
−3stability
3 －
4 >increases
−[OMs] >[Br]
>in [Br]
the >>>[TFA]
order [TFA] [Tau] －
the － stability
)) For
increases [OTf] >acid
[PTS] >the SO [OMs]
(Table 12 choline based amino ILs, stability increases − − > [Br]−
－ (Table ILs,
12 stability
choline increases
based amino in the
－－ (Table 12 ) For choline based amino acid ILs, the stability increases in the order [Tau]
order ILs, [OTf]
the > [PTS]
stability increases > [CH inin
3 SO the
the order
4 ]order [OMs] [Tau]
[Tau] －－
－
－

(Table
(Table 12>)[TFA] 12 ) For
For choline −choline
(Tablebased based
12) For amino
amino choline acid
acidbased ILs,
ILs, the the stability
stability
amino increases
acidincreases
ILs, the stability in the
in the order order
increases [Tau]
[Tau]in the order
[Tau]− > [Threo]− > [β-ala]− [77]. For fatty acid ILs, the stability increases in the order
oleate > linoleate > caprylate > caproate [121]. The influence of anions on the thermal
9,
9, xx FOR
FOR PEER
PEER REVIEW
REVIEW 21
21 of
of 36
36
Processes 2021, 9, 337 21 of 36
9, x FOR PEER REVIEW 21 of 36

Processes 2021, 9,
Processes 9, x FOR PEER
PEER REVIEW
REVIEW 21 of 36
36
Processes 2021,
2021, 9, xx FOR
FOR PEER
－
REVIEW － 21
21 of
of 36
－ －
>> [Threo]
[Threo]－－ >> [β-ala] [77].
[77]. For
[β-ala]－－stability Forfor fatty
fatty acid
acid ILs,
ILs, the
the stability
stability increases
increases in in the
the order
order oleate
oleate >
>linoleate
[Threo]>> caprylate
> [β-ala] [77]. For fattyotheracid cations
ILs, has
the been compared
stability increases in
in detail
the by Xue
order oleate et >>al. [122]. In general,
linoleate caprylate ILs > caproate
> caproate [121].
[121]. The
− The influence of anions on the thermal stability for
with [NTf [BFinfluence
2 ] －,The
−
4 ] or [PFof
of]−anions
perform
6 anions
on the thermal
better in heat stability
resistance,for and imidazolium,
linoleate
other
other－cations > caprylate
cations has
has been
> > caproate
compared
[Threo]
been
－ [121].
－ > [β-ala]
compared
－ in
in detail
－ [77].
detail
－ influence
by
by Xue
For
Xue et
fatty
et al.
al. [122].
acid
[122]. In
ILs, on
In the
general,
the thermal
ILs
stability
general, ILs stability
with [NTf
increases
with [NTf in ]]－－－,,the order oleate >
22for
> [Threo]
pyrrolidinium,
>been
[Threo] > [β-ala]
> [β-ala] and [77]. For
pyridinium
[77]. fatty acid
are ILs, the
considered stability
as cationsincreases
with in2
excellentthe
the order oleate
thermal >>
oleatestabil-
other －
[BF444]]－cations
[BF or [PF666has
or [PF
－
]]－－ perform
perform compared
linoleate better
better
> caprylateininheat
in
caprylate detail
heat byForXuefatty
> resistance,
resistance,
caproate al.acid
etand
and
[121].
ILs,
[122]. Inthe
imidazolium,
imidazolium,
The influence
stability
general, ILs increases
withon
pyrrolidinium,
pyrrolidinium,
of anions
anions [NTf in
2] ,
theand
and
－ order
thermal stability
stability forfor
－ － linoleate
ity >
[34,63,122].
linoleatebetter>ascaprylate > caproate
> resistance,
caproate [121].
[121]. The
The influence
influence of on
of anions on theand the thermal
thermal stability for
[BF 4]
pyridinium
pyridinium or [PFare 6] considered
are perform
other cations
considered in heat
as cations
cations has
cations beenwith
with excellent
compared
excellentin and imidazolium,
inthermal
detail
thermal stability
by Xue et
stability pyrrolidinium,
et[34,63,122].
al. [122].
[122]. In
[34,63,122]. In general,
general, ILs ILs with [NTf22]]－－－,,
with [NTf
other
other cations has
has been
been compared
compared in detail
detail by
by Xue
Xue et al.
al. [122]. In general, ILs with [NTf 2] ,
pyridinium are considered [BFTable
4]－
－
－ or
as
[PF cations
6]－
－
－ perform
with excellent
better in thermal
inILs
heat stabilityand [34,63,122].
[BF
[BF 44]
] or
or [PF
10.
[PF 66]
Tonset
] perform better
of 1,2,4-triazolium
perform better in heat
heat aresistance,
at resistance,
heating rate
resistance, and
andof 10 imidazolium,
◦ C/min in nitrogen
imidazolium,
imidazolium,
pyrrolidinium,
pyrrolidinium,
atmosphereand
pyrrolidinium,
and
and[78].
Table
Table 10. 10. T
Tonset of 1,2,4-triazolium ILs
onset of 1,2,4-triazolium
at
at aa heating
heating rate
ILsconsidered rate of
of 10
10 °C/min
°C/min in
in nitrogen atmosphere
nitrogenthermal
atmosphere [78].
[78]. [34,63,122].
onset
pyridinium
pyridinium are as cations with excellent stability
pyridinium are
Table 10. Tonset of 1,2,4-triazolium areILsconsidered
at a heating as
considered ratecations
as cations with
with excellent
of 10 °C/min excellent
in nitrogen thermal
thermal
atmosphere stability
[78]. [34,63,122].
stability [34,63,122].
ILs Structure of Anions Tonset /◦ C
ILs
ILs Structure of
Structure of AnionsAnions T onset/°C
Tonset/°C
onset
Table 10. ILsTTonset ofof 1,2,4-triazolium ILs ILs at aaStructure
heating rate of 10
10 °C/min in in nitrogen
nitrogen atmosphere [78].
Table
Table 10. 10. onset of 1,2,4-triazolium
Tonset 1,2,4-triazolium ILs at at a heating rateofof
heating rate ofAnions
°C/min in T
10 °C/min onset/°C atmosphere
nitrogen atmosphere [78].
[78].
4-methyl-1-propyl-1,2,4-
ILs
ILs Structure 365
Structure of Anions
Anions Tonset
onset/°C
4-methyl-1-propyl-1,2,4-triazolium
triazolium[NTf
4-methyl-1-propyl-1,2,4-triazolium ILs 222]]
[NTf Structure of T /°C
365Anions 365 Tonset/°C
of
[NTf2 ] [NTf2]
4-methyl-1-propyl-1,2,4-triazolium 365
4-methyl-1-propyl-1,2,4-triazolium [NTf22]]
4-methyl-1-propyl-1,2,4-triazolium 365
4-methyl-1-propyl-1,2,4-triazolium [NTf
[NTf2] 365
365
4-methyl-1-propyl-1,2,4-
4-methyl-1-propyl-1,2,4-triazolium
triazolium [OTf]
4-methyl-1-propyl-1,2,4-triazolium [OTf] 330
330 330
4-methyl-1-propyl-1,2,4-triazolium
[OTf] [OTf] 330
4-methyl-1-propyl-1,2,4-triazolium [OTf]
4-methyl-1-propyl-1,2,4-triazolium 330
4-methyl-1-propyl-1,2,4-triazolium [OTf]
[OTf] 330
330
4-methyl-1-propyl-1,2,4-
4-methyl-1-propyl-1,2,4-triazolium
triazolium [BF
4-methyl-1-propyl-1,2,4-triazolium [BF444]] 302
302 302
4-methyl-1-propyl-1,2,4-triazolium
[BF4 ] [BF4] 302
4-methyl-1-propyl-1,2,4-triazolium [BF44]]
4-methyl-1-propyl-1,2,4-triazolium 302
4-methyl-1-propyl-1,2,4-triazolium [BF
[BF4] 302
302
4-methyl-1-propyl-1,2,4-
4-methyl-1-propyl-1,2,4-triazolium
triazolium [PTs]
4-methyl-1-propyl-1,2,4-triazolium [PTs] 291
291 291
4-methyl-1-propyl-1,2,4-triazolium
[PTs] [PTs] 291
4-methyl-1-propyl-1,2,4-triazolium [PTs]
4-methyl-1-propyl-1,2,4-triazolium 291
4-methyl-1-propyl-1,2,4-triazolium [PTs]
[PTs] 291
291
4-methyl-1-propyl-1,2,4-
4-methyl-1-propyl-1,2,4-triazolium
triazolium[OMs]
4-methyl-1-propyl-1,2,4-triazolium [OMs] 267
267 267
4-methyl-1-propyl-1,2,4-triazolium
[OMs] [OMs] 267
4-methyl-1-propyl-1,2,4-triazolium [OMs]
4-methyl-1-propyl-1,2,4-triazolium
4-methyl-1-propyl-1,2,4-triazolium[I] [OMs] 267
267
4-methyl-1-propyl-1,2,4-triazolium
4-methyl-1-propyl-1,2,4-triazolium[I]
4-methyl-1-propyl-1,2,4- [OMs] I-
I- 207
207 267
4-methyl-1-propyl-1,2,4-triazolium[I] I-
I- 207 207
triazolium[I]
4-methyl-1-propyl-1,2,4-triazolium[I]
4-methyl-1-propyl-1,2,4-triazolium[I]
4-methyl-1-propyl-1,2,4-triazolium [NO I-
I- 207
207
[NO333]]
4-methyl-1-propyl-1,2,4-triazolium[I]
4-methyl-1-propyl-1,2,4-
4-methyl-1-propyl-1,2,4-triazolium I-198
198 207
4-methyl-1-propyl-1,2,4-triazolium
triazolium[NO3] 198 198
[NO3 ]
4-methyl-1-propyl-1,2,4-triazolium [NO33]]
4-methyl-1-propyl-1,2,4-triazolium 198
4-methyl-1-propyl-1,2,4-triazolium [NO
[NO3] 198
198
Table
Table 11.
11. T T5% of tributyltetradecyl phosphonium ILs at a heating rate of 10 °C/min in nitrogen
5% of tributyltetradecyl phosphonium ILs at a heating rate of 10 °C/min in nitrogen
5%
atmosphere
Table 11. T5%[37].
atmosphere of tributyltetradecyl phosphonium ILs at a heating rate of 10 °C/min in nitrogen
[37].
atmosphere [37]. Table 11. T5% of tributyltetradecyl phosphonium ILs at a heating rate of 10 ◦ C/min in nitrogen
ILs Table 11.
11. T5%
5% of tributyltetradecyl
Structure phosphonium
of ILs at aa heating
heating rate of
of 10
10 °C/min in nitrogen
nitrogen
ILs Table
Table 11. T
T5% of
atmosphere tributyltetradecyl
of [37]. Structure
tributyltetradecyl of Anions
phosphonium
Anions ILs
phosphonium ILs at rate ofT
at a heating rate T10
5%/°C
°C/min
°C/min in
5%/°C
5%
in nitrogen
ILs atmosphere
atmosphere [37]. Structure of Anions T5%/°C
atmosphere [37].
[37].
[P4,4,4,14][PFOS] ILs ILs Structure of Anions
Structure of Anions 426 T5% /◦T
C5%/°C
[P 4,4,4,14][PFOS]
[P4,4,4,14 ][PFOS] ILs
ILs Structure
Structure of
of Anions
Anions 426
426 T 5%/°C
T5% /°C
[P4,4,4,14][PFOS] 426
[P4,4,4,14][PFOS]
[P ][PFOS]
[P4,4,4,14 ][PFOS] 426
426 426
[P4,4,4,14
4,4,4,14][PFOS] 426
[P
[P4,4,4,14 ][NPf2]
4,4,4,14][NPf22]
4,4,4,14 418
418
[P4,4,4,14][NPf2] 418
[P4,4,4,14][NPf
[P ][NPf 2]
22]
[P4,4,4,14 418
418 418
[P4,4,4,14
4,4,4,14][NPf ] ][NPf2 ] 418
[P 4,4,4,14][NTf
[P4,4,4,14
4,4,4,14 ][NTf222]] 405
405
[P4,4,4,14][NTf2] 405
[P4,4,4,14][NTf
[P ][NTf22]] 405
[P4,4,4,14
4,4,4,14][NTf 2] ][NTf2 ]
[P4,4,4,14 405 405
405
[P 4,4,4,14][FeCl
[P4,4,4,14
4,4,4,14 ][FeCl444]] 401
401
[P4,4,4,14][FeCl4] 401
[P4,4,4,14][FeCl
[P ][FeCl4] 401
4,4,4,14][FeCl44]
[P4,4,4,14 ] 401
401
 [P4,4,4,14][PFOS] 426

Processes 2021, 9, 337 22 of 36

[P4,4,4,14][NPf2] 418

Table 11. Cont.

[P4,4,4,14][NTf2] 405
ILs Structure of Anions T5% /◦ C

Processes
Processes 2021,2021, 9, x FOR
9, x FOR PEER
PEER REVIEW
REVIEW 22 of22
36of 36
[P4,4,4,14][FeCl 4] ][FeCl4 ]
[P4,4,4,14 401 401

Processes 2021,
Processes 2021, 9,
9, x
x FOR
FOR PEER
PEER REVIEW
REVIEW 22 of
22 of 36
36
Processes 2021, 9, x FOR PEER REVIEW 22 of 36

[P4,4,4,14
[P4,4,4,14 ][AOT]
[P4,4,4,14
][AOT] ][AOT] 330 330330

[P4,4,4,14
[P
[P 4,4,4,14 ][AOT]
][AOT]
4,4,4,14][AOT]
4,4,4,14
330
330
330
[P4,4,4,14
[P4,4,4,14 ][OS]
[P ][OS]
4,4,4,14 ][OS] 194 194194

[P4,4,4,14
[P
[P 4,4,4,14 ][OS]
][OS]
4,4,4,14][OS]
4,4,4,14
194
194
194
Table
Table 12. The
12. The thermal
thermal decomposition
decomposition temperature
temperature of nitrile-functionalized
of nitrile-functionalized azepanium
azepanium ILsa at a
ILs at
heating
Table
heating 12. rate
rate The
of 10ofthermal
10 °C/min
°C/min in ininert
an an inert
decomposition atmosphere
temperature
atmosphere [123].
[123]. of nitrile-functionalized azepanium ILs at a
heatingTable
rate of12. ◦ C/min in an inert atmosphere [123].
10The thermal decomposition
decomposition temperature of nitrile-functionalized
nitrile-functionalized azepanium ILs ILs at
at aaa
ILs ILs
Table
Table 12. The
12. The thermal
thermal Structure
decomposition
Structure oftemperature
Anions Decomposition
temperature
of Anions of
of Decomposition Temperature/°C
nitrile-functionalized azepanium
azepanium
Temperature/°C ILs at
heating rate
heating rate
heating of
rate of 10
of 10 °C/min
10 °C/min in
°C/min in an
in an inert
an inert atmosphere
inert atmosphere [123].
atmosphere [123].
[123]. Decomposition
ILs Structure of Anions ◦C
ILs Structure of Anions Temperature/
Decomposition Temperature/°C
ILs
ILs Structure of
Structure of Anions
Anions Decomposition Temperature/°C
Decomposition Temperature/°C
[C4CNAzp][OTf]
[C4CNAzp][OTf] 332332

[C4444CNAzp][OTf]
[C
[C CNAzp][OTf]
[C4 CNAzp][OTf]
CNAzp][OTf] 332
332
332
332

[C4CNAzp][PTs]
[C4CNAzp][PTs] 240240

[C4444CNAzp][PTs]
[C
[C CNAzp][PTs]
[C4 CNAzp][PTs]
CNAzp][PTs] 240
240
240
240

[C4CNAzp][CH
[C4CNAzp][CH 3SO34SO
] 4] 234234

[C4444CNAzp][CH
[C
[C CNAzp][CH
CNAzp][CH 33SO44]
SO44]] 234
234
[C4 CNAzp][CH 3 SO4 ]33SO 234
234

[C4CNAzp][OMs]
[C4CNAzp][OMs] 220220

[C4444CNAzp][OMs]
[C
[C CNAzp][OMs]
CNAzp][OMs]
[C44CNAzp][Br]
CNAzp][OMs] 220
220
220
220
[C
[C4CNAzp][Br] Br- Br- 216216

[C4444CNAzp][Br]
[C
[C CNAzp][Br]
CNAzp][Br]
[C4 CNAzp][Br] Br-
Br-
Br-
Br- 216
216
216
216
[C4CNAzp][TFA]
[C4CNAzp][TFA] 176176

[C4444CNAzp][TFA]
[C
[C CNAzp][TFA]
CNAzp][TFA]
[C4 CNAzp][TFA] 176
176
176
176

5. Thermal
5. Thermal Stability
Stability of Some
of Some Novel Novel ILs ILs
5.1.5.1.
ILs ILs Mixtures
Mixtures
5.
5. Thermal
Preparing
5. Thermal
Thermal
Preparing ILStability
mixtures
Stability
Stability
IL mixtures of
of
isof Some
aisSome
Some a simpler
simpler Novel
andand
Novel
Novel ILs
ILs
ILs
more more promising
promising approach
approach compared
compared with with
5. Thermal Stability of Some Novel ILs
developing 5.1.
developing
5.1. ILs
new Mixtures
newILs.
ILs Mixtures ILs.
Mixtures Figure Figure 15 15
shows shows TGA TGA curves curvesof of binary
binary mixtures
mixtures with with
differentdifferent
5.1. ILs5.1. ILs
Mixtures
proportions
proportions of4IM][BF
[C4IM][BF
ofPreparing
[C IL 4],4IM][NO
[C4IM][NO
4], mixtures
[C is3a], [C3],4MIM][BF
[C4MIM][BF and4]more4] and
and [C [C4MIM][NO
4MIM][NO 3] [124].
3] [124]. It can
Itcompared
can be be with
Preparing
Preparing
Preparing ILthe IL
IL
mixtures mixtures
mixtures
isstability
a simpler is
is aa simpler
simpler
simpler
and more and
and more
more promising
promising
promising
promising approach
approach
approach
approach
compared compared
comparedwith with
with
concluded
concluded that
that the thermal
developing thermal
new ILs. stability
ILs. Figureof15 of
15binary binary
showsmixtures mixtures
TGA curves is determined
is determined
curves by
binarybymixtures
of binary the
the ILs which
mixtures ILs which
with different
different
developing
developing
developing new
new
new ILs. Figure ILs. Figure
Figure 15 shows
shows TGA
TGA curves of
of binary mixtures with
with different
could
could be reconstituted
beproportions
reconstituted by44IM][BF
of [C
[C all all15ions
by ions 4],in
shows
4in
[Cthe the
IM][NO
TGA mixture
mixture
curves
3], [C [125].
of binary
[125]. In44]other
In other
MIM][BF and
mixtures
words,
words,
[C 4MIM][NO
withanions
the the
anions
different
andand
3] [124]. It can
can be
be
proportions
proportions
proportions of [C 4 of
of [C
IM][BF IM][BF
44IM][BF
4 ], [C 4 ], [C
44],
4IM][NO[C IM][NO
444IM][NO
3 ], [C [C4444MIM][BF
],], [C
333MIM][BF
4 MIM][BF
4 ] and44]] [C
and
and4 [C
[C MIM][NO
444MIM][NO
MIM][NO 3 ] 333]] [124].
[124]. [124]. It
It
It can can be
cations
cations can can combine
combine
concluded that freely
freely
that the in
the thermalin
the the
mixture
thermal stability mixture [111,112].
[111,112].
stability of of binary
binary mixtures
mixtures is is determined
determined by by the the ILs
ILs which
which
concluded
concluded that the thermal stability of binary mixtures is determined by the ILs which
could
could be
could be reconstituted
be reconstituted
reconstituted by by
by all all ions
all ions
ions in in the
in the mixture
the mixture [125].
mixture [125].
[125]. In In other
In other words,
other words,
words, the the anions
the anions
anions andand
and
cations
cations can
cations can combine
can combine
combine freely freely
freely in in the
in the mixture
the mixture
mixture [111,112].[111,112].
[111,112].
 Processes 2021, 9, 337 23 of 36

be concluded that the thermal stability of binary mixtures is determined by the ILs which
s 2021, 9, x FOR PEER REVIEW 23 of 36
could be reconstituted by all ions in the mixture [125]. In other words, the anions and
cations can combine freely in the mixture [111,112].

Figure 15. Figure

TGA 15. TGAof
curves curves of binary
binary mixtures
mixtures with different
with different ILs and
ILs and proportions
proportions at aatheating
a heating 10 ◦ C/min in
rateofof10
rate
°C/min in nitrogen
nitrogen atmosphere [124]. atmosphere [124].

In order to predict the thermal

In order stability
to predict of mixtures,
the thermal Navarro
stability et al. [126]
of mixtures, proposed
Navarro a
et al. [126] proposed a
method to obtain the mass loss of IL mixtures at different temperatures by using pure ILs
method to obtain the mass loss of IL mixtures at different temperatures by using pure ILs
TGA data as TGA data as
L
mmixture = ∑ wl ·ml (30)
𝑚 = 𝑤 ∙𝑚 l =1 (30)
where mmixture is the mass that the mixture would lose in an ideal case at each temperature,
where 𝑚 ml isdenotes
the mass the that
experimental
the mixture masswould
loss oflosespecies
in an in ideal
formingcasetheatmixture
each at a certain
temperature, 𝑚temperature,
denotes thewexperimental
l refers to the mass
mass fraction
loss of of the
species lth
in component
forming thein the
mixture mixture,
at and L is the
a certain temperature, 𝑤 refers to the mass fraction of the lth component in the mixture,
number of compounds involved in the mixture. This method has successfully predicted
and 𝐿 is the number of compounds involved in the mixture. This method has successfully
the thermal stability of several IL binary mixtures [80,126,127]. However, for the mixture of
[4C4 MPyr][NTf
predicted the thermal stability 2of] and [C2 MIM][EtSO
several 4 ], the model
IL binary mixtures cannot However,
[80,126,127]. predict its for thermal
the stability well,
− anion and the other
mixture of [4C4and this may
MPyr][NTf 2] be
andrelated to the strong
[C2MIM][EtSO 4], the interaction
model cannotbetween [EtSO
predict its4 ]thermal
ionsthis
stability well, and in the
maymixture
be related[128].
to the strong interaction between [EtSO4]- anion and
In addition,
the other ions in the mixture [128]. the study has revealed that mixing certain ILs in an appropriate ratio can
improve thermal stability.
In addition, the study has revealed that TGA datacertain
mixing of mixtures
ILs in of
an[C 4 MIM][NTf
appropriate 2 ] and
ratio can[C8 MIM][AcO]
in different proportions proves that when the
improve thermal stability. TGA data of mixtures of [C4MIM][NTf2] and [C8MIM][AcO] mole fraction of [C MIM][AcO]
8 in is be-
tween 0.1 and
different proportions proves that when 0.3, T and T
5% the mole are significantly higher than
10% fraction of [C8MIM][AcO] is between 0.1 the values predicted by
and 0.3, T5% and Equation
T10% are(30)significantly
[64]. The resultshigherofthan
nuclearthe magnetic resonance
values predicted by (NMR)
Equation indicate that the
(30)[64]. The results of nuclear magnetic resonance (NMR) indicate that the synergistic as the main
synergistic role of hydrogen bond and electrostatic interactions are proposed
role of hydrogen reason
bondfor andtheelectrostatic
improvement of the thermal
interactions stability of
are proposed as the
the IL mixtures.
main reason for
the improvement of the thermal stability of the IL mixtures.

5.2. Dicationic ILs

Due to their unique properties, dicationic ILs (DILs) have been widely used in
thermal storage [67,129], organic synthesis [130], anti-corrosion [131], or as surface-active
agents [132], and they are less toxic than their monocationic counterparts [133].
Processes 2021, 9, 337 24 of 36

5.2. Dicationic ILs

Processes 2021, 9, x FOR PEER REVIEW 24 of 36
Due to their unique properties, dicationic ILs (DILs) have been widely used in ther-
mal storage [67,129], organic synthesis [130], anti-corrosion [131], or as surface-active
agents [132], and they are less toxic than their monocationic counterparts [133].
The
The Tonset
onsetof
of monocationic
monocationic ILs [C [C1010MIM][Br],
MIM][Br], [C12 12MIM][Br]
MIM][Br] andand [C14 14MIM][Br],
MIM][Br], and
dicationic
dicationicILsILs[C[C10(MIM)
10 (MIM) 2][Br]
2 2, [C12
][Br] 2, (MIM)
[C 12 2][Br]
(MIM) 2 2 and [C
][Br] 2 and 14(MIM)
[C 14 2][Br]2,][Br]
(MIM) 2 are shown in Figure
2 are shown
, in
16. The 16.
Figure valuesTheof values
DILs areof30-40 DILs°Care higher
30-40 ◦ C their
than monocationic
higher than their counterparts
monocationic[134–136].
counter-
Other studies have
parts [134–136]. obtained
Other studies similar
haveconclusions, whichconclusions,
obtained similar are ascribedwhichto higher charges,
are ascribed
higher molecular
to higher charges, weight,
higherand greater intermolecular
molecular weight, and greater interactions of DILs [6,129,137].
intermolecular interactions Due
of
to their
DILs stronger electrostatic
[6,129,137]. Due to theirinteractions, DILs often
stronger electrostatic demonstrate
interactions, higher
DILs melting
often points
demonstrate
than monocationic
higher melting points ILs,than
which limits theirILs,
monocationic applications
which limits [69]. Therefore,
their numerous
applications methods
[69]. Therefore,
numerous
of loweringmethods of lowering
melting points have beenmelting points have
proposed, such been proposed,
as adjusting suchlinkage
alkane as adjusting
chain
alkane linkage
length, changing chain length,
cationic headchanging
groupscationic head groups
and anions, mixing and
DILs anions, mixing
with the same DILs with
cationic
the same cationic head groups and anion but different alkane linkage
head groups and anion but different alkane linkage chains [37], utilizing branched alkane chains [37], utilizing
branched
linkage alkane
chains [69]linkage chains [69]
and designing and designingDILs
unsymmetrical unsymmetrical
[138]. DILs [138].

Figure 16. Tonset of [Cn MIM][Br] and [Cn (MIM)2 ][Br]2 obtained by TGA at a heating rate of
10 ◦ C/min in nitrogen atmosphere [134] (n = 10, 12, 14).
Figure 16. Tonset of [CnMIM][Br] and [Cn(MIM)2][Br]2 obtained by TGA at a heating rate of 10
°C/min in nitrogen atmosphere [134] (n = 10,12,14).
As shown in Table 13, when the linkage chain is the same, the thermal stability of DILs
withAs cationic
shownhead groups
in Table 13, of (MMIM),
when (C1 Py),
the linkage and is
chain (PC 3 Csame,
the 3 C3 ) isthe
significantly different.
thermal stability of
Moreover, Figure 17 suggests that the longer the alkyl side chains are, the lower the
DILs with cationic head groups of (MMIM), (C1Py), and (PC3C3C3) is significantly
thermal stability of DILs are. The reduced thermal stability is attributed to the decreasing
different. Moreover, Figure 17 suggests that the longer the alkyl side chains are, the lower
symmetry of cations with the increase of the number of carbon atoms in the alkyl side
the thermal stability of DILs are. The reduced thermal stability is attributed to the
chains, which hinders the crystal effective accumulation [129,139]. Table 14 demonstrates
decreasing symmetry of cations with the increase of the number of carbon atoms in the
that the decomposition temperatures of DILs with some functional groups are higher
alkyl side chains, which hinders the crystal effective accumulation [129,139]. Table 14
than those of DILs without corresponding functional groups. This might be explained by
demonstrates that the decomposition temperatures of DILs with some functional groups
the appearance of complex functional groups increasing the strength of intermolecular
are higher than those of DILs without corresponding functional groups. This might be
interaction and the energy of chemical bonds [139].
explained by the appearance of complex functional groups increasing the strength of
intermolecular interaction and the energy of chemical bonds [139].
 Processes 2021, 9, 337 25 of 36
Processes
Processes 2021,
2021, 9, x FOR PEER REVIEW 25 of 36
Processes 2021,
Processes 9,9,xx xFOR
2021, 9,FOR
FOR PEER
PEER REVIEW
REVIEW 2525of
ofof
3636
Processes
Processes 2021,
2021,
Processes 9,
9, x 9,
2021, FORxxFOR
FOR
PEER
PEERPEER REVIEW
REVIEW
REVIEW
PEER REVIEW 25 25
25 of2536 of36
36of 36

Table13.
Processes 2021, 9, x FOR PEER REVIEW
Table Thermalstability
13.Thermal stability
ofof dicationic
dicationic ILsILs (DILs)
(DILs) containing
containing different
different cationic
cationic head
head groups
25groups
of 36 at aat a
Table
Table 13.Thermal
13.
Table
Table 13. Thermal
Thermal
13. Thermal stability
stability ofofdicationic
stability
stability of dicationic
dicationic
of ILs(DILs)
ILs
dicationic
ILs (DILs)
(DILs)
ILs containing
containing
(DILs) different
different
containing
containing cationic
cationic
different
different head
head
cationic
cationic head groups
groups
head
groups atataa aat a
groups
at
Table 13. 13.
Table
heating
heating Thermal
rateThermal
rate of 10 ◦
of 10stability
C/min
°C/min ofindicationic
stability of ILs ILs
dicationic
nitrogen
in nitrogen (DILs)
atmosphere
atmosphere containing
(DILs)
[69]. different
containing
[69]. cationic
different head
cationic groups
head at aat a
groups
heating
heating raterate
rate
heating
heating rate ofof10
of 1010 °C/min
°C/min
of°C/min
10 ininnitrogen
°C/min
in nitrogen
nitrogen atmosphere
atmosphere
innitrogen
nitrogen [69].
[69].
atmosphere
atmosphere [69]. [69].
heating raterate
heating of 10of °C/min
10 in nitrogen
°C/min in atmosphere
atmosphere[69].[69].
DILs Structure of Cations ◦ C/°C T T0.05 ◦ C/°C TT0.15//°C◦C
DILs
DILsstability of dicationic
DILs
Table 13. Thermal DILs
Structure
Structure
Structure of
ILs (DILs) of Cations
ofCations
Cations
containing
Structure ofCations
Cations TTT
differentTcationic
T
0.01 /0.01
0.01
/°C/°C TT
0.05
head groups/0.05
/°C/°C
at a TT
0.15
0.15 /°C
/°C
DILs Structure of
of Cations TT
/°C0.01/°C T0.05T
T/°C0.05/°C
T0.15TT 0.15/°C
/°C
0.01 0.05 0.15
DILs
DILs
heating rate of 10
Structure
Structure
°C/min in nitrogen atmosphere [69].
Cations
of T0.01
0.01 /°C
0.01/°C T0.05 /°C
0.05/°CT0.15 /°C
0.15/°C

[C
[C 32M(MMIM)2][NTf2]2
32M(MMIM)
398 438 478
[C
[C 2M(MMIM)
3[C 3 2M(MMIM)
[C 32M(MMIM)
[C332M(MMIM)
2M(MMIM) 22][NTf
][NTf
][NTf
DILs 222][NTf
][NTf 2][NTf]2222]]22 2]2 Structure of Cations
222]
]2 2]2 T0.01/°C398
398
398398398
398398
438
438
T0.05/°C438
438 438
T0.15
438 /°C 478
478478
478
478
478478
[C 32M(MMIM) 2][NTf 438
[C32M(MMIM)2][NTf2]2 398 438 478
[C
[C
[C 32M(C1Py)2][NTf2]2
32M(C
2M(C 1Py)
Py) 2][NTf
][NTf ]2222]]22 2]2 313
313313 373
313 373
373373
373 401
401401
401
[C
[C[C [C
3332M(C
2M(C
[C 32M(C
111Py)
3 2M(C
32M(C Py) 122Py)
1 Py)2][NTf
1Py)
2][NTf
2 ][NTf
][NTf 222]
2][NTf ]2 2]2 313
313
313313 373
373373 401
401
401401
[C32M(C1Py)2][NTf2]2 313 373 401
[C
[C
[C 32M(PC3C3C3)2][NTf2]2
32M(PC
2M(PC C3C C33C )][NTf
2][NTf ]222]2 2]2 355
355355 402
402402 434
434434
[C
[C[C [C
3332M(PC
2M(PC
[C 32M(PC
333C
32M(PC
3 2M(PC
3C
C3 3C
3C
33CC )))332232C
333C ][NTf
C )22][NTf
)233)][NTf
3][NTf
][NTf
222]
]22]22]2
355
355
355355
355
402
402
402402
402
434
434
434
434434
[C32M(PC3C3C3)2][NTf2]2 355 402 434
325
325325 325
325325
325
325 325
325
325 325 320
320320
320
325 325
320
325
320
320
320
320320 325 320
320320
320
320 320 320
320 320 320 320 320
320
315 320 315
315315
315 315315
315
315
315 315 315
315 315
315
310 309
309309
309
315
310
310310
310
310 311
311311 309
309309 310310
310
310
310 310 311
311 309 310 310
310
305 311311
311
310
305
305305
305 305305
305
305 305 305

(℃)
305 305 305305
305 305 305
(℃)

onset(℃)
305 305
305

(℃)
(℃)

(℃)
(℃)

305305

(℃)
305
(℃)
(℃)

300 300

(℃)
(℃)
Tonset (℃)
(℃)
TT10% (℃)

300300 300300
(℃)

300
300 300
300
300 300
300 299 300 300 300
10%

299

onset
299 299

Tonset
10%

299299
T10%

onset
onset
295 295
10%

299292
10%

299

onset
TTonset
295295 295295
10%
10%

295 295
295
295
295 295 292
292
292292 292 295 295
295 295

T
TT

TTT
TTT

290 292292 290

290
290
290290 290 290290
290
290
290 290 290
290 290
285 285
285
285
285285
285
285 285
281 285
281281
281 281
281
285285
285
285
285 285
280 281281 280
280
280
280 280 280280
280
280 280
280 280 280
280 280
280 280
280 280
275
280 280
280280 275
275
275275 275 275275
275
275 275
275
275 275 275 275
270
270 270 270
270270
270 270270
270
270
270 270 000 11 2 22 3 3 4 44 270
270 270
1 33 3
00
0 00 11
1 11 22 2 44
4 44
Alkyl chain length, n 33 3
2 2
Alkyl chain length, n
Alkyl
Alkyl chain
chain
Alkyl
Alkyl chain
chain length,
length, nn n
length,
length, n
Figure
Figure17. 17.Thermal decomposition Alkyl
Alkyl chain
temperaturechainlength,
length,
of [C 2(Cnof
n [C
IM) 2n][Br]
Figure 17.
Thermal
Thermal
decomposition
decomposition
temperature
temperature of [C 2 (C2nand IM)[C 4(CnIM)
2 ][Br] 2 and
2(CnIM)2][Br]2 and [C4(CnIM)2][Br]2 at a
2][Br][C2 at(C
4 a n IM)2 ][Br]2 at a
Figure
Figure
Figure
Figure 17.
17.rate
heating
17. Thermal
Thermal
17. ofThermal
Thermal 1010 decomposition
decomposition
°C/min
◦ C/minin nitrogen
decomposition
decomposition temperature
temperature
atmosphere
temperature
temperature of
of [C [C
[Cof
[129,139]
of (C
2(C2 (C
(n
[C nIM)
IM)
2=
nIM)(C1–4). 2][Br]
][Br]
n22IM)
][Br] 2 and
and
2=][Br]
2 and [C[C
2 and
[C 4(C4(C
(C[C nIM)
IM) 2][Br]
][Br]
4(Cn22IM)
nIM) 2][Br]
2 at
at
222 at a aat a
heating
Figure
Figure
heating rate
17.rate
Thermal
17. of
Thermal
of 10 in
decomposition nitrogen
decomposition
°C/min in nitrogen atmosphere
temperature
temperature
atmosphere of [C [129,139]
2
of2(C
[129,139] n
[Cn2IM)
(CnIM)(n (n
2][Br] 2 1–4).
2 and
][Br]
==21–4). 4
[C4(C
2 and
n
[Cn4IM)
(CnIM)2][Br]
][Br]
2][Br] at a2a2at a
heating
heating
heatingrate
rate ofof
rate 1010 °C/min
°C/min
of°C/min
10°C/min in
°C/min in nitrogen
nitrogen
innitrogen atmosphere
atmosphere
nitrogen atmosphere [129,139]
[129,139]
[129,139] (n (n = 1–4).
1–4).
(n
heating
heating rate of
of 10
raterate
heating 10
of °C/min
10 in
in nitrogen
nitrogen
in atmosphere
atmosphere
atmosphere [129,139]
[129,139]
[129,139] (n
(n ==(n ==1–4).
1–4).
1–4). 1–4).
Table
Table14.14.Tonset of DILs
Tonset with different
of DILs functional
with different groups at agroups
functional heating rate at aofheating
10 °C/min ratein nitrogen
of 10 ◦ C/min in
Table 14.
atmosphere
Table 14.T T
T onset
[139]. of
of DILs
DILs with
with different
different functional
functional groups
groups at
at aa heating
heating rate
rate of
of 10
10 °C/min
°C/min in nitrogen
ininnitrogen
nitrogen
Table
Table
14.
14. T
Table
nitrogen
Table 14.
Table
atmosphere T onset
14.
14. T
onset
onsetTonset
onsetof
atmosphere
of DILs
of DILs
onset
[139]. DILs
of
with
ofDILs
DILs
[139].
with
with
different
with
different
different
with
functional
different
functional
functional
different
groups
functional
groups
groups
functional groups
groups
at
at a
at aaat
heating
at aaheating
heating
heating
rate
heating
rate of
rate
of
of 10
raterate
10
10
of
°C/min
of°C/min
10°C/min
°C/min
10 °C/min in nitrogen
innitrogen
in nitrogen
in nitrogen
atmosphere
atmosphere
atmosphere
atmosphere [139].
[139].
ILs
[139]. [139]. Structure of Cations T onset/°C
atmosphere
atmosphere [139].
[139].
ILsILs Structure
Structure of ofCations
Cations Tonset /◦ C /°C
Tonset
ILsILs
ILs Structure
Structure ofofCations
Structure Cations
Cations
of Cations TT T/°C
onset/°C
onset/°C
[C4(CILs Structure of 277.33T /°C
onset
ILsILs
2IM) 2][Br]2 Structure of Cations
Structure of Cations Tonset /°C/°C
Tonset
onset

[C
[C (CIM)
4[C
4(C
IM)
2(C
2IM)
2][Br]
2 IM) 2 ][Br]
2][Br]
2 2 277.33
277.33
277.33
[C
[C 4(C
[C44(C
(C
[C[C22244IM)
IM)
(C2IM)
][Br]
4(C222IM)
2][Br]
][Br]2][Br]
222
2][Br]
2
2
2 277.33 277.33
277.33
277.33
277.33
[C4(C2H4IM)2][Br]2 304.36

[C
[C
[C 4(C2H4IM)2][Br]2
(C
4[C
4(C H
2(C IM)2][Br]
H IM)2][Br] 304.36
304.36
304.36
4H IM)2][Br]
224H 304.36
2 2
[C [C
[C44(C
(C
[C H
2224
4H
(C
(C
4IM)2][Br]
444IM)2][Br]
2IM)2][Br]
222
H44IM)2][Br] 2
2 304.36
304.36
304.36
304.36
[C4(C2H5OIM)2][Br]2 297.65

[C
[C
[C 4(C2H5OIM)2][Br]2
4(C
4(C 2H 5OIM) 2][Br]
297.65
297.65
4H OIM) ][Br] 297.65
2
[C [C22244H
[C44(C
(C
[C H(C
(C555OIM)
22HH555OIM)
2OIM)
OIM)
222][Br]
OIM) ][Br] ][Br]
222
2][Br]
22][Br] 222 297.65 297.65
297.65
297.65
297.65
[C4(C2H3O2IM)2][Br]2 309.43

[C
[C
[C 4(C2H3O2IM)2][Br]2
4(C
4(C 2H 3O 2IM) 2][Br]
309.43
309.43
4H O 2IM) ][Br] 309.43
2
[C44(C
[C [C2224H
(C (C
333O 2H 3O222IM)
H223IM) 2][Br]
2][Br]
222 2 309.43
309.43
[C
[C 4H(C
(C 2O
2H IM)
3O ][Br]
O22IM)
IM) 22][Br]
][Br] 22 309.43
309.43309.43
Processes 2021, 9, 337 26 of 36

The change of the linkage chain between the two cationic head groups also has an
important influence on thermal stability. The linkage chain is usually a straight-chain alkyl,
and a longer linkage chain leads to worse thermal stability within a certain range, while a
further increase in chain length leads to the decrease of thermal stability [37]. DILs with the
branched linkage chain are developed due to reducing the high melting point of DILs with
a straight linkage chain. Although the thermal stability of DILs containing the branched
alkyl linkage chain is lower than their linear counterparts, it should be noted that this
discrepancy is acceptable when the length of the linkage chain reaches C5 . Therefore, the
thermal stability of DILs can be tuned by branching linkage chains [69]. Recently, DILs with
m-xylyl, pyridine functional groups, and dioxane linkage chain have been synthesized,
and all of them have a low melting point and high thermal stability [140–142]. Similar
to monocationic ILs, anions have a major influence in the thermal stability of DILs, and
Table 15 reveals that the thermal stability order is as follows: [NTf2 ]− > [PF6 ]− >[BF4 ]−
> [OTf]− > [Cl]− [129,141]. The [NTf2 ]− DILs also have high thermal stability and low
melting point [37,138,140]. Generally, the influence factors of DILs structure on thermal
stability are similar to monocationic ILs. Therefore, the properties of DILs that have not
been determined by experiments can be inferred from the known monocationic ILs.

Table 15. The decomposition temperature of DILs with different anions at a heating rate of 10 ◦ C/min
in nitrogen atmosphere [129,141]. Reproduced with permission from Jianlian Liu, Journal of Molecular
Liquids; published by Elsevier, 2020; reproduced with permission from Coby J. Clarke, ACS Sustainable
Chemistry & Engineering; published by American Chemical Society, 2020.

DILs Decomposition Temperature/◦ C

[Pyri(C8 MIM)2 ][Cl]2 273.2 a
[Pyri(C8 MIM)2 ][OTf]2 417.8 a
[Pyri(C8 MIM)2 ][BF4 ]2 419.1 a
[Pyri(C8 MIM)2 ][PF6 ]2 429.4 a
[Pyri(C8 MIM)2 ][NTf2 ]2 443.5 a
[C4 (MIM)2 ][BF4 ]2 384.6 b
[C4 (MIM)2 ][PF6 ]2 423.4 b
[C4 (MIM)2 ][NTf2 ]2 468.1 b
a Tonset from [141]; b T10% from [129].

6. Summary
The methods measuring the thermal stability of ILs are discussed. Although Tonset
overestimates the thermal stability, it is still used as a universal parameter in different
investigations. It should be noted that when using Tonset to compare the thermal stability it
is necessary to determine whether the experimental conditions (atmosphere type, heating
rate, etc.) are the same. Although Tz/y is defined as a parameter to measure the long-
term thermal stability of ILs, it is clear that this parameter cannot meet the required
time of industrial running. Thus, a series of methods have been proposed to predict the
thermal stability of ILs over a longer period. Among them, MOT is considered a highly
accurate method, and the activation energy and pre-exponential factor values in the thermal
decomposition process are required for calculating MOT.
Different means to study the thermal degradation kinetics of ILs are elaborated. After
extensively analyzing the kinetic data from several investigations, it can be concluded
that the isoconversional methods have been widely used to calculate the activation energy
values, and the results of integral isoconversional methods are more accurate than those
of differential methods. In addition, maximum-rate methods and Arrhenius methods
are used in many research studies due to their simple calculation process, although both
methods are not as precise as isoconversional methods. The Arrhenius method is also used
to calculate the pre-exponential factor. However, compensation effect or master plots are
seen lately as reliable tools for calculating pre-exponential factor values.
Processes 2021, 9, 337 27 of 36

Thermal stability data of divergent ILs are summarized in Table 16 according to the
types of anions, and this table reveals many structural factors affecting thermal stability,
in which the modification of cations is the prime research object. For cations, a longer
alkyl side chain, functionalization, and the bonding of alkyl chain via tertiary carbon atom
all reduce the thermal stability of ILs. In the process of etherification, the number and
position of oxygen atoms and the length of the O–alkyl chain have evident effects on
thermal stability. Moreover, due to the high acidity of the C2 proton, methyl substitution in
the C2 position on the imidazolium ring can improve the thermal stability. Although there
are many methods to change the thermal stability by tuning cations, it should be stressed
that the type of anions plays a major role in determining thermal stability. Generally,
some specific anions such as [NTf2 ]− , [BF4 ]− , and [PF6 ]− and cations such as imidazolium,
pyrrolidinium, and pyridinium make the ILs more stable at high temperatures.

Table 16. Decomposition temperature and activation energy of some ILs and DILs.

No. ILs Tonset /◦ C T5% /◦ C T10% /◦ C Tpeak /◦ C E/kJ mol−1 Ref.

Monocationic ILs
263 122 a [57]
1 [C2 MIM][Cl]
260 120 b [39]
2 [C3 MIM][Cl] 246 155 a [57]
260 151 a [57]
3 [C4 MIM][Cl]
250 105 b [39]
4 [C4 MMIM][Cl] 267 58.688 b [86]
5 [C6 MIM][Cl] 253 98 a [57]
6 [C10 MIM][Cl] 247 150 a [57]
7 [C3 OHMIM][Cl] 295 [113]
8 [P6,6,6,14 ][Cl] 320 [40]
9 [C2 MIM][Br] 283 125 b [39]
10 [C4 MIM][Br] 255 127 b [39]
11 [C10 MIM][Br] 265 298 [134]
12 [C12 MIM][Br] 257 292 [134]
13 [C14 MIM][Br] 255 287 [134]
14 [C2 NH2 MIM][Br] 222 [113]
15 [C4CN Azp][Br] 216 [123]
16 [C2 MIM][I] 279 111 b [39]
17 [C4 MIM][I] 265 121 b [39]
18 [C3 MT1,2,4 M][I] 207 188 122.1 c [78]
19 [C2 MIM][NTf2 ] 425 384 402 470 102 b ; 108 d [44]
406 358 379 448 92 b ; 98 d [44]
20 [C3 MIM][NTf2 ]
412 369 115.8 c [78]
426 385 405 466 125 b ; 130 d [44]
421 478 [58]
21 [C4 MIM][NTf2 ]
367 465 115.9 b ;121.3 d ; 116.3 a [18]
418 385 130.7 c [75]
418 374 394 468 119 b ; 124 d [44]
22 [C4 MMIM][NTf2 ]
436 408 478 129 c [47]
23 [C7 MIM][NTf2 ] 437 426 464 [110]
24 [C12 MIM][NTf2 ] 405 418 464 125 b [49]
25 [N4,4,4,1 ][NTf2 ] 380 374 435 121 b [49]
26 [N8,8,8,1 ][NTf2 ] 362 386 425 108 b [49]
27 [P4,4,4,14 ][NTf2 ] 405 [37]
28 [C3 MPy][NTf2 ] 469 [72]
29 [C4 MPy][NTf2 ] 451 [66] 450 128.6 d ; 123.6 b ; 124.0 a [50]
30 [C5 MPy][NTf2 ] 443 [72]
Processes 2021, 9, 337 28 of 36

Table 16. Cont.

No. ILs Tonset /◦ C T5% /◦ C T10% /◦ C Tpeak /◦ C E/kJ mol−1 Ref.

31 [C6 MPy][NTf2 ] 440 [72]
32 [C7 MPy][NTf2 ] 429 [72]
33 [C8 MPy][NTf2 ] 443 [66] 447 [50] 113.7 d ; 107.8 b ; 108.2 a [50]
34 [C9 MPy][NTf2 ] 447 [72]
35 [C10 MPy][NTf2 ] 421 [72]
36 [C1 OC2 MPy][NTf2 ] 411 399 443 [63]
37 [C2 MT1,2,4 M][NTf2 ] e 355 327 102.5 c [75]
38 [C3 MT1,2,4 M][NTf2 ] e 365 337 110.3 c [75]
39 [C4 MT1,2,4 M][NTf2 ] e 350 327 114.8 c [75]
40 [C6 MT1,2,4 M][NTf2 ] e 345 318 119.1 c [75]
41 [C8 MT1,2,4 M][NTf2 ] e 346 318 123.6 c [75]
42 [C10 MT1,2,4 M][NTf2 ] e 357 331 127.7 c [75]
43 [C12 MT1,2,4 M][NTf2 ] e 354 326 131.6 c [75]
44 [BnzMIM][NTf2 ] 421 402 464 [110]
45 [(Bnz)2 IM][NTf2 ] 410 391 453 [110]
46 [NapmMIM][NTf2 ] 406 392 460 [110]
47 [PP16 ][NTf2 ] 385 [117]
48 [PP1EP ][NTf2 ] 349 [117]
49 [PP1PE ][NTf2 ] 348 [117]
50 [PP1MB ][NTf2 ] 314 [117]
51 [PP1MEM ][NTf2 ] 268 [117]
52 [PP1BM ][NTf2 ] 259 [117]
53 [PP1MEEM ][NTf2 ] 253 [117]
54 [ethoxyC5 IM][NTf2 ] 377.3 [66]
55 [ethoxyiC5 IM][NTf2 ] 372.7 [66]
56 [ethoxyneoC5 IM][NTf2 ] 369.8 [66]
57 [ethoxycC5 IM][NTf2 ] 355.4 [66]
58 [ethoxy3C5 IM][NTf2 ] 354.3 [66]
59 [C4 C5 IM][NTf2 ] 413.2 [66]
60 [C4 iC5 IM][NTf2 ] 402.3 [66]
61 [C4 cC5 IM][NTf2 ] 365.9 [66]
62 [C4 3C5 IM][NTf2 ] 362.9 [66]
63 [C4 MIM][PTs] 346 379 [58]
64 [C3 MT1,2,4 M][PTs] e 291 271 141.8 c [78]
65 [C4CN Azp][PTs] 240 [123]
66 [Chol][Tos] 332 346 [73]
67 [C2 Py][Tos] 335 357 [73]
68 [Chol][Ac] 200 222 [73]
69 [C2 MIM][Ac] 221 [85]
70 [C4 MIM][OS] 314 353 [58]
71 [P4,4,4,14 ][OS] 194 [37]
72 [MIM][NO3 ] 163 184 112.7 d [90]
73 [C3 MT1,2,4 M][NO3 ] e 198 187 132.1 c [78]
74 [C3 MT1,2,4 M][OMs] e 267 254 138.9 c [78]
75 [C4CN Azp][OMs] 220 [123]
76 [C4 MIM][OTf] 382 420 [58]
77 [C4 MMIM][OTf] f 436 424 479 148 c [47]
78 [C3 MT1,2,4 M][OTf] e 365 337 110.3 c [78]
79 [C4CN Azp][OTf] 332 [123]
80 [C4 MIM][BF4 ] 381 396 [58]
81 [C2 MMIM][BF4 ] 391 [101]
82 [C2 NH2 MMIM][BF4 ] 284 72.2 c [101]
83 [C3 MT1,2,4 M][BF4 ] e 302 264 102.2 c [78]
84 [C1 OC2 MPy][(C2 F5 )3 PF3 ] 352 349 384 [63]
85 [P6,6,6,14 ][(C2 F5 )3 PF3 ] 363 356 396 [63]
Processes 2021, 9, 337 29 of 36

Table 16. Cont.

No. ILs Tonset /◦ C T5% /◦ C T10% /◦ C Tpeak /◦ C E/kJ mol−1 Ref.

274 293 [58]
86 [C4 MIM][DBP]
286 157.88 a [56]
87 [C4 MIM][AcO] 222 246 [58]
88 [P6,6,6,14 ][AcO] 275.8 259.3 [83]
89 [P6,6,6,14 ][ButO] 270.6 248.3 [83]
90 [P6,6,6,14 ][HexO] 255.8 233.9 [83]
91 [P6,6,6,14 ][OctO] 242.8 219.6 [83]
92 [P6,6,6,14 ][DecO] 268.8 260.4 [83]
93 [P4,4,4,8 ][BScB] 412 430 [81]
94 [P4,4,4,8 ][BMB] 403 430 [81]
95 [Chol][H2 PO4 ] 246 335 [73]
96 [C4 MIM][HSO4 ] 348 389 [58]
97 [C4 MIM][SbF6 ] 387 413 [58]
98 [C4 MIM][PF6 ] 412 386 399 461 100.60 b ; 107.36 d [55]
99 [BSMBIM][CF3 SO3 ] 331 359 171.01 b ; 171.30 a [54]
100 [C4 MMIM][FAP] 376 379 402 139 c [47]
101 [P4,4,4,14 ][PFOS] 426 [37]
102 [P4,4,4,14 ][NPf2 ] 418 [37]
103 [P4,4,4,14 ][FeCl4 ] 401 [37]
104 [P4,4,4,14 ][AOT] 330 [37]
105 [C4CN Azp][CH3 SO4 ] 234 [123]
106 [C4CN Azp][TFA] 176 [123]
Dicationic ILs
107 [C2 (MIM)2 ][Br]2 311 [139]
108 [C2 (C2 IM)2 ][Br]2 305 [139]
109 [C2 (C3 IM)2 ][Br]2 299 [139]
110 [C2 (C4 IM)2 ][Br]2 280 [139]
111 [C4 (C2 IM)2 ][Br]2 277 [139]
112 [C10 (MIM)2 ][Br]2 299 317 [134]
113 [C12 (MIM)2 ][Br]2 289 309 [134]
114 [C14 (MIM)2 ][Br]2 294 315 [134]
115 [C4 (C2 H4 IM)2 ][Br]2 304 [139]
116 [C4 (C2 H5 OIM)2 ][Br]2 298 [139]
117 [C4 (C2 H3 O2 IM)2 ][Br]2 309 [139]
118 [C4 (MIM)2 ][Br]2 320 [129]
119 [C4 (C2 IM)2 ][Br]2 309 [129]
120 [C4 (C3 IM)2 ][Br]2 299 [129]
121 [C4 (C4 IM)2 ][Br]2 281 [129]
122 [Pyri(C8 MIM)2 ][Cl]2 273 [141]
123 [Pyri(C8 MIM)2 ][OTf]2 418 [141]
124 [Pyri(C8 MIM)2 ][PF6 ]2 429 [141]
125 [C4 (MIM)2 ][PF6 ]2 423 [129]
126 [C4 (MIM)2 ][NTf2 ]2 468 [129]
127 [C3 2M(MMIM)2 ][NTf2 ]2 438 [69]
128 [C3 2M(C1 Py)2 ][NTf2 ]2 373 [69]
129 [C3 2M(PC3 C3 C3 )2 ][NTf2 ]2 402 [69]
130 [Pyri(C8 MIM)2 ][NTf2 ]2 444 [141]
All TGA experiments were performed under an N2 atmosphere and at a heating rate of 10 ◦ C/ min unless indicated. In ref. [44,63,85,90]
an air atmosphere was used, and in ref. [66], an argon atmosphere was used. In ref. [56,90] the heating rate was 8 ◦ C/min, and in
ref. [83], the heating rate was 5 ◦ C/min. a Starink method; b KAS method; c zero-order Arrhenius method; d Flynn–Wall–Ozawa (FWO)
method; e T1,2,4 M denotes 1,2,4-triazolium; f in the air atmosphere; reproduced with permission from Asli Akçay, Thermochimica Acta;
published by Elsevier, 2014; reproduced with permission from Wenlong Wang, Chemical Engineering Journal; published by Elsevier, 2017;
reproduced with permission from Andreah T. De La Hoz, The Journal of Physical Chemistry B; published by American Chemical Society, 2014;
reproduced with permission from Josefa Salgado, The Journal of Chemical Thermodynamics; published by Elsevier, 2013; reproduced with
permission from Samuel M. Murray, Journal of Chemical & Engineering Data; published by American Chemical Society, 2013; reproduced
with permission from D. Blanco, Thermochimica Acta; published by Elsevier, 2017; reproduced with permission from Rahul A. Patil,
Chemistry of Materials; published by American Chemical Society, 2016; reproduced with permission from Gebrekidan Gebresilassie Eshetu,
ChemSusChem; published by Wiley, 2017; reproduced with permission from Khurrum Shehzad Quraishi, Journal of Thermal Analysis and
Calorimetry; published by Springer Nature, 2017; reproduced with permission from Juan J. Parajó, The Journal of Chemical Thermodynamics;
Processes 2021, 9, 337 30 of 36

published by Elsevier, 2018; reproduced with permission from T. Nokami, Faraday Discussions; published by Royal Society of Chemistry,
2018; reproduced with permission from Jan Rotrekl, Fluid Phase Equilibria; published by Elsevier, 2020; reproduced with permission from
J.J.Parajó, The Journal of Chemical Thermodynamics; published by Elsevier, 2020; reproduced with permission from Nana Yamaki, Journal of
Thermal Analysis and Calorimetry; published by Springer Nature, 2019; reproduced with permission from Vikranth Volli, Journal of Thermal
Analysis and Calorimetry; published by Springer Nature, 2019; reproduced with permission from Shuangyue Liu, Journal of Molecular
Liquids; published by Elsevier, 2015; reproduced with permission from Hui-Chun Jiang, Journal of Thermal Analysis and Calorimetry;
published by Springer Nature, 2019; reproduced with permission from K. Oster, The Journal of Chemical Thermodynamics; published by
Elsevier, 2018; reproduced with permission from Faiz Ullah Shah, Molecules; published by Molecular Diversity Preservation International,
2020; reproduced with permission from Zhen Huang, Journal of Thermal Analysis and Calorimetry; published by Springer Nature, 2019;
reproduced with permission from Zahoor Ullah, Procedia Engineering; published by Elsevier, 2016; reproduced with permission from Hang
Zhang, The Journal of Physical Chemistry C; published by American Chemical Society, 2018; reproduced with permission from Jianlian Liu,
Journal of Molecular Liquids; published by Elsevier, 2020; reproduced with permission from Coby J. Clarke, ACS Sustainable Chemistry &
Engineering; published by American Chemical Society, 2020; reproduced with permission from Mohsen Talebi, Journal of Molecular Liquids;
published by Elsevier, 2018.

Finally, the thermal stability of some novel ILs is introduced to provide more choices
in high-temperature applications. In ILs mixtures, the anions and cations can combine
freely. It is also feasible to predict the thermal stability of ILs mixtures by using TGA data
of pure ILs. DILs have better thermal stability than their monocationic counterparts, and
the influence factors of DILs structure on thermal stability are similar to monocationic ILs.
Moreover, due to the stronger electrostatic interactions, DILs have a higher melting point,
while adjusting the length of the linkage chain and the type of anions can obtain DILs with
low melting point and high thermal stability.

Author Contributions: Conceptualization, C.X. and Z.C.; writing—review and editing, C.X.; review
and editing, Z.C. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the National Natural Science Foundation of China (No.
21676085) and the National Key R&D Program of China (No. 2019YFC1906705).
Data Availability Statement: Data sharing not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

Nomenclature

A Pre-exponential factor, min−1

Aα Isoconversional values of pre-exponential factor, min−1
E Activation energy, kJ mol−1
Eα Isoconversional values of the activation energy, kJ mol−1
f (α) Kinetic model function
g(α) Integral kinetic model function
k(T ) Rate constant
L Number of compounds presented in the mixture
m Mass at a certain time
m1 End mass of the sample
m0 Initial mass
ml Experimental mass loss of each IL forming the mixture at each temperature
mmixture Mixture mass lose in an ideal case at each temperature
MOT Maximum operating temperature, ◦ C
R Universal gas constant, 8.314 J mol−1 K−1
tmax Maximum operation time
Tonset Onset decomposition temperature, ◦ C
Tpeak Temperature of maximum degradation, ◦ C
T50% Temperature at the decomposition degree of 50%, ◦ C
Tz Temperature at the decomposition degree z, ◦ C
T0.01/10h Temperature at decomposition degree of 0.01 within 10 h, ◦ C
Processes 2021, 9, 337 31 of 36

Tz/y Temperature at decomposition degree z within the selected time y, ◦ C

T(dw/dT 6=0) Temperature at which the first appreciable weight loss occurs, K
wl Each IL mass fraction in the mixture
Greek Symbols
α Extent of conversion
β Heating rate, ◦ C min−1
Subscripts
α Different extent of conversion
i Different temperature programs
j All heating programs other than i

References
1. Egorova, K.S.; Ananikov, V.P. Fundamental Importance of Ionic Interactions in the Liquid Phase: A Review of Recent Studies of
Ionic Liquids in Biomedical and Pharmaceutical Applications. J. Mol. Liq. 2018, 272, 271–300. [CrossRef]
2. Qiao, Y.; Ma, W.; Theyssen, N.; Chen, C.; Hou, Z. Temperature-Responsive Ionic Liquids: Fundamental Behaviors and Catalytic
Applications. Chem. Rev. 2017, 117, 6881–6928. [CrossRef]
3. Boruń, A. Conductance and Ionic Association of Selected Imidazolium Ionic Liquids in Various Solvents: A Review. J. Mol. Liq.
2019, 276, 214–224. [CrossRef]
4. Ichikawa, T.; Kato, T.; Ohno, H. Dimension Control of Ionic Liquids. Chem. Commun. 2019, 55, 8205–8214. [CrossRef]
5. Jiang, S.; Hu, Y.; Wang, Y.; Wang, X. Viscosity of Typical Room-Temperature Ionic Liquids: A Critical Review. J. Phys. Chem. Ref.
Data 2019, 48, 033101. [CrossRef]
6. Götz, M.; Reimert, R.; Bajohr, S.; Schnetzer, H.; Wimberg, J.; Schubert, T.J.S. Long-Term Thermal Stability of Selected Ionic Liquids
in Nitrogen and Hydrogen Atmosphere. Thermochim. Acta 2015, 600, 82–88. [CrossRef]
7. Amde, M.; Liu, J.-F.; Pang, L. Environmental Application, Fate, Effects, and Concerns of Ionic Liquids: A Review. Environ. Sci.
Technol. 2015, 49, 12611–12627. [CrossRef] [PubMed]
8. Ghandi, K. A Review of Ionic Liquids, Their Limits and Applications. Green Sustain. Chem. 2014, 4, 44–53. [CrossRef]
9. Rybińska-Fryca, A.; Mikolajczyk, A.; Łuczak, J.; Paszkiewicz-Gawron, M.; Paszkiewicz, M.; Zaleska-Medynska, A.; Puzyn, T.
How Thermal Stability of Ionic Liquids Leads to More Efficient TiO2 -Based Nanophotocatalysts: Theoretical and Experimental
Studies. J. Colloid Interface Sci. 2020, 572, 396–407. [CrossRef]
10. Elhamifar, D.; Kazempoor, S.; Karimi, B. Amine-Functionalized Ionic Liquid-Based Mesoporous Organosilica as a Highly Efficient
Nanocatalyst for the Knoevenagel Condensation. Catal. Sci. Technol. 2016, 6, 4318–4326. [CrossRef]
11. Giacalone, F.; Gruttadauria, M. Covalently Supported Ionic Liquid Phases: An Advanced Class of Recyclable Catalytic Systems.
ChemCatChem 2016, 8, 664–684. [CrossRef]
12. Oh, Y.-H.; Jang, H.B.; Im, S.; Song, M.J.; Kim, S.-Y.; Park, S.-W.; Chi, D.Y.; Song, C.E.; Lee, S. SN2 Fluorination Reactions in Ionic
Liquids: A Mechanistic Study towards Solvent Engineering. Org. Biomol. Chem. 2010, 9, 418–422. [CrossRef] [PubMed]
13. Bouvet, S.; Pégot, B.; Marrot, J.; Magnier, E. Solvent Free Nucleophilic Introduction of Fluorine with [Bmim][F]. Tetrahedron Lett.
2014, 55, 826–829. [CrossRef]
14. Newington, I.; Perez-Arlandis, J.M.; Welton, T. Ionic Liquids as Designer Solvents for Nucleophilic Aromatic Substitutions. Org.
Lett. 2007, 9, 5247–5250. [CrossRef] [PubMed]
15. Khan, A.S.; Man, Z.; Bustam, M.A.; Kait, C.F.; Ullah, Z.; Nasrullah, A.; Khan, M.I.; Gonfa, G.; Ahmad, P.; Muhammad, N. Kinetics
and Thermodynamic Parameters of Ionic Liquid Pretreated Rubber Wood Biomass. J. Mol. Liq. 2016, 223, 754–762. [CrossRef]
16. Reina, L.; Botto, E.; Mantero, C.; Moyna, P.; Menéndez, P. Production of Second Generation Ethanol Using Eucalyptus Dunnii
Bark Residues and Ionic Liquid Pretreatment. Biomass Bioenergy 2016, 93, 116–121. [CrossRef]
17. Gregorio, G.F.D.; Weber, C.C.; Gräsvik, J.; Welton, T.; Brandt, A.; Hallett, J.P. Mechanistic Insights into Lignin Depolymerisation in
Acidic Ionic Liquids. Green Chem. 2016, 18, 5456–5465. [CrossRef]
18. Wang, W.; Ma, X.; Grimes, S.; Cai, H.; Zhang, M. Study on the Absorbability, Regeneration Characteristics and Thermal Stability
of Ionic Liquids for VOCs Removal. Chem. Eng. J. 2017, 328, 353–359. [CrossRef]
19. Zhang, W.; Ye, L.; Jiang, J. CO2 Capture with Complex Absorbent of Ionic Liquid, Surfactant and Water. J. Environ. Chem. Eng.
2015, 3, 227–232. [CrossRef]
20. Faghihi-Zarandi, A.; Shirkhanloo, H.; Jamshidzadeh, C. A New Method for Removal of Hazardous Toluene Vapor from Air
Based on Ionic Liquid-Phase Adsorbent. Int. J. Environ. Sci. Technol. 2019, 16, 2797–2808. [CrossRef]
21. G˛ebicki, J.; Kloskowski, A.; Chrzanowski, W.; Stepnowski, P.; Namiesnik, J. Application of Ionic Liquids in Amperometric Gas
Sensors. Crit. Rev. Anal. Chem. 2016, 46, 122–138. [CrossRef] [PubMed]
22. Yin, K.; Zhang, Z.; Li, X.; Yang, L.; Tachibana, K.; Hirano, S. Polymer Electrolytes Based on Dicationic Polymeric Ionic Liquids:
Application in Lithium Metal Batteries. J. Mater. Chem. A 2014, 3, 170–178. [CrossRef]
23. Varela, J.C.; Sankar, K.; Hino, A.; Lin, X.; Chang, W.; Coker, D.; Grinstaff, M. Piperidinium Ionic Liquids as Electrolyte Solvents
for Sustained High Temperature Supercapacitor Operation. Chem. Commun. 2018, 54, 5590–5593. [CrossRef] [PubMed]
24. Kasprzak, D.; St˛epniak, I.; Galiński, M. Acetate- and Lactate-Based Ionic Liquids: Synthesis, Characterisation and Electrochemical
Properties. J. Mol. Liq. 2018, 264, 233–241. [CrossRef]
Processes 2021, 9, 337 32 of 36

25. Wang, X.; Jin, M.; Li, Y.; Zhao, L. The Influence of Various Ionic Liquids on the Properties of SPEEK Membrane Doped with
Mesoporous Silica. Electrochim. Acta 2017, 257, 290–300. [CrossRef]
26. Wu, H.; Shen, F.; Wang, J.; Wan, Y. Membrane Fouling in Vacuum Membrane Distillation for Ionic Liquid Recycling: Interaction
Energy Analysis with the XDLVO Approach. J. Membr. Sci. 2018, 550, 436–447. [CrossRef]
27. Pizzoccaro-Zilamy, M.-A.; Drobek, M.; Petit, E.; Totée, C.; Silly, G.; Guerrero, G.; Cowan, M.G.; Ayral, A.; Julbe, A. Initial Steps
toward the Development of Grafted Ionic Liquid Membranes for the Selective Transport of CO2 . Ind. Eng. Chem. Res. 2018, 57,
16027–16040. [CrossRef]
28. Huang, G.; Yu, Q.; Cai, M.; Zhou, F.; Liu, W. Investigation of the Lubricity and Antiwear Behavior of Guanidinium Ionic Liquids
at High Temperature. Tribol. Int. 2017, 114, 65–76. [CrossRef]
29. Lee, J.; Yeo, C.-D.; Hu, Z.; Thalangama-Arachchige, V.D.; Kaur, J.; Quitevis, E.L.; Kumar, G.; Koh, Y.P.; Simon, S. Friction and
Wear of Pd-Rich Amorphous Alloy (Pd43Cu27Ni10P20) with Ionic Liquid (IL) as Lubricant at High Temperatures. Metals 2019,
9, 1180. [CrossRef]
30. Li, Y.; Zhang, S.; Ding, Q.; Feng, D.; Qin, B.; Hu, L. The Corrosion and Lubrication Properties of 2-Mercaptobenzothiazole
Functionalized Ionic Liquids for Bronze. Tribol. Int. 2017, 114, 121–131. [CrossRef]
31. Kaur, N. Green Synthesis of Three- to Five-Membered O-Heterocycles Using Ionic Liquids. Synth. Commun. 2018,
48, 1588–1613. [CrossRef]
32. Liu, J.; Wang, F.; Zhang, L.; Fang, X.; Zhang, Z. Thermodynamic Properties and Thermal Stability of Ionic Liquid-Based Nanofluids
Containing Graphene as Advanced Heat Transfer Fluids for Medium-to-High-Temperature Applications. Renew. Energy 2014,
63, 519–523. [CrossRef]
33. Wang, W.; Wu, Z.; Li, B.; Sundén, B. A Review on Molten-Salt-Based and Ionic-Liquid-Based Nanofluids for Medium-to-High
Temperature Heat Transfer. J. Therm. Anal. Calorim. 2019, 136, 1037–1051. [CrossRef]
34. Lamas, A.; Brito, I.; Salazar, F.; Graber, T.A. Synthesis and Characterization of Physical, Thermal and Thermodynamic Properties
of Ionic Liquids Based on [C12mim] and [N444H] Cations for Thermal Energy Storage. J. Mol. Liq. 2016, 224, 999–1007. [CrossRef]
35. Mehrkesh, A.; Karunanithi, A.T. Optimal Design of Ionic Liquids for Thermal Energy Storage. Comput. Chem. Eng. 2016,
93, 402–412. [CrossRef]
36. Williams, M.L.; Holahan, S.P.; McCorkill, M.E.; Dickmann, J.S.; Kiran, E. Thermal and Spectral Characterization and Stability of
Mixtures of Ionic Liquids [EMIM]Ac and [BMIM]Ac with Ethanol, Methanol, and Water at Ambient Conditions and at Elevated
Temperatures and Pressures. Thermochim. Acta 2018, 669, 126–139. [CrossRef]
37. Patil, R.A.; Talebi, M.; Xu, C.; Bhawal, S.S.; Armstrong, D.W. Synthesis of Thermally Stable Geminal Dicationic Ionic Liquids
and Related Ionic Compounds: An Examination of Physicochemical Properties by Structural Modification. Chem. Mater. 2016,
28, 4315–4323. [CrossRef]
38. Odugbesi, G.A.; Nan, H.; Soltani, M.; Davis, J.H.; Anderson, J.L. Ultra-High Thermal Stability Perarylated Ionic Liquids as Gas
Chromatographic Stationary Phases for the Selective Separation of Polyaromatic Hydrocarbons and Polychlorinated Biphenyls. J.
Chromatogr. A 2019, 1604, 460466. [CrossRef] [PubMed]
39. Efimova, A.; Varga, J.; Matuschek, G.; Saraji-Bozorgzad, M.R.; Denner, T.; Zimmermann, R.; Schmidt, P. Thermal Resilience
of Imidazolium-Based Ionic Liquids—Studies on Short- and Long-Term Thermal Stability and Decomposition Mechanism of
1-Alkyl-3-Methylimidazolium Halides by Thermal Analysis and Single-Photon Ionization Time-of-Flight Mass Spectrometry. J.
Phys. Chem. B 2018, 122, 8738–8749. [CrossRef]
40. Deferm, C.; van den Bossche, A.; Luyten, J.; Oosterhof, H.; Fransaer, J.; Binnemans, K. Thermal Stability of Trihexyl(Tetradecyl)Phosphonium
Chloride. Phys. Chem. Chem. Phys. 2018, 20, 2444–2456. [CrossRef] [PubMed]
41. Patil, R.A.; Talebi, M.; Berthod, A.; Armstrong, D.W. Dicationic Ionic Liquid Thermal Decomposition Pathways. Anal. Bioanal.
Chem. 2018, 410, 4645–4655. [CrossRef] [PubMed]
42. Soltani, M.; Siu, B.; Salter, E.A.; Wierzbicki, A.; West, K.N.; Davis, J.H. Synthesis, Thermal Stability, and Computed Bond
Dissociation Energies of Tetraarylphosphonium-Based Mesothermal Ionic Liquids Bearing a Quinoline Ring System. Tetrahedron
Lett. 2017, 58, 4628–4631. [CrossRef]
43. Siu, B.; Cassity, C.G.; Benchea, A.; Hamby, T.; Hendrich, J.; Strickland, K.J.; Wierzbicki, A.; Sykora, R.E.; Salter, E.A.;
O’Brien, R.A.; et al. Thermally Robust: Triarylsulfonium Ionic Liquids Stable in Air for 90 Days at 300 ◦ C. RSC Adv. 2017,
7, 7623–7630. [CrossRef]
44. Parajó, J.J.; Teijeira, T.; Fernández, J.; Salgado, J.; Villanueva, M. Thermal Stability of Some Imidazolium [NTf 2 ] Ionic
Liquids: Isothermal and Dynamic Kinetic Study through Thermogravimetric Procedures. J. Chem. Thermodyn. 2017,
112, 105–113. [CrossRef]
45. Maton, C.; Vos, N.D.; Stevens, C.V. Ionic Liquid Thermal Stabilities: Decomposition Mechanisms and Analysis Tools. Chem. Soc.
Rev. 2013, 42, 5963–5977. [CrossRef]
46. Al-Sallami, W.; Parsaeian, P.; Neville, A. An Appraisal of the Thermal Decomposition Mechanisms of ILs as Potential Lubricants.
Lubr. Sci. 2019, 31, 229–238. [CrossRef]
47. Salgado, J.; Villanueva, M.; Parajó, J.J.; Fernández, J. Long-Term Thermal Stability of Five Imidazolium Ionic Liquids. J. Chem.
Thermodyn. 2013, 65, 184–190. [CrossRef]
48. Blanco, D.; Bartolomé, M.; Ramajo, B.; Viesca, J.L.; González, R.; Hernández Battez, A. Isoconversional Kinetic Analysis Applied
to Five Phosphonium Cation-Based Ionic Liquids. Thermochim. Acta 2017, 648, 62–74. [CrossRef]
Processes 2021, 9, 337 33 of 36

49. Blanco, D.; Oulego, P.; Ramos, D.; Fernández, B.; Cuetos, J.M. Model-Free Kinetics Applied to Evaluate the Long-Term Thermal
Stability of Three [NTf2] Anion-Based Ionic Liquids. Thermochim. Acta 2017, 656, 70–84. [CrossRef]
50. Seeberger, A.; Andresen, A.-K.; Jess, A. Prediction of Long-Term Stability of Ionic Liquids at Elevated Temperatures by Means of
Non-Isothermal Thermogravimetrical Analysis. Phys. Chem. Chem. Phys. 2009, 11, 9375. [CrossRef] [PubMed]
51. Salgado, J.; Parajó, J.J.; Fernández, J.; Villanueva, M. Long-Term Thermal Stability of Some 1-Butyl-1-Methylpyrrolidinium Ionic
Liquids. J. Chem. Thermodyn. 2014, 74, 51–57. [CrossRef]
52. Wooster, T.J.; Johanson, K.M.; Fraser, K.J.; MacFarlane, D.R.; Scott, J.L. Thermal Degradation of Cyano Containing Ionic Liquids.
Green Chem. 2006, 8, 691. [CrossRef]
53. Quraishi, K.S.; Bustam, M.A.; Krishnan, S.; Khan, M.I.; Wilfred, C.D.; Lévêque, J.-M. Thermokinetics of Alkyl Methylpyrrolidinium
[NTf2] Ionic Liquids: Effect of Alkyl Chain on Thermal Stability. J. Therm. Anal. Calorim. 2017, 129, 261–270. [CrossRef]
54. Ullah, Z.; Bustam, M.A.; Man, Z.; Khan, A.S. Thermal Stability and Kinetic Study of Benzimidazolium Based Ionic Liquid. Procedia
Eng. 2016, 148, 215–222. [CrossRef]
55. Huang, Z.; Wang, X.; Lu, T.; Nong, D.; Zhao, J.; Wei, M.; Teng, L.; Teng, L. Isoconversional Kinetic Analysis of Thermal
Decomposition of 1-Butyl-3-Methylimidazolium Hexafluorophosphate under Inert Nitrogen and Oxidative Air Atmospheres. J.
Therm. Anal. Calorim. 2019, 140, 695–712. [CrossRef]
56. Jiang, H.-C.; Lin, W.-C.; Hua, M.; Pan, X.-H.; Shu, C.-M.; Jiang, J.-C. Analysis of Thermal Stability and Pyrolysis Kinetic of Dibutyl
Phosphate-Based Ionic Liquid through Thermogravimetry, Gas Chromatography/Mass Spectrometry, and Fourier Transform
Infrared Spectrometry. J. Therm. Anal. Calorim. 2019, 138, 489–499. [CrossRef]
57. Williams, M.L.; Dickmann, J.S.; McCorkill, M.E.; Hassler, J.C.; Kiran, E. The Kinetics of Thermal Decomposition of 1-Alkyl-
3-Methylimidazolium Chloride Ionic Liquids under Isothermal and Non-Isothermal Conditions. Thermochim. Acta 2020,
685, 178509. [CrossRef]
58. Akçay, A.; Balci, V.; Uzun, A. Structural Factors Controlling Thermal Stability of Imidazolium Ionic Liquids with 1- n -Butyl-3-
Methylimidazolium Cation on γ-Al 2 O 3. Thermochim. Acta 2014, 589, 131–136. [CrossRef]
59. Makhoukhi, B.; Villemin, D.; Didi, M.A. Synthesis of Bisimidazolium–Ionic Liquids: Characterization, Thermal Stability and
Application to Bentonite Intercalation. J. Taibah Univ. Sci. 2016, 10, 168–180. [CrossRef]
60. Mezzetta, A.; Łuczak, J.; Woch, J.; Chiappe, C.; Nowicki, J.; Guazzelli, L. Surface Active Fatty Acid ILs: Influence of the Hydropho-
bic Tail and/or the Imidazolium Hydroxyl Functionalization on Aggregates Formation. J. Mol. Liq. 2019, 289, 111155. [CrossRef]
61. Song, Y.; Xia, Y.; Liu, Z. Influence of Cation Structure on Physicochemical and Antiwear Properties of Hydroxyl-Functionalized
Imidazolium Bis(Trifluoromethylsulfonyl)Imide Ionic Liquids. Tribol. Trans. 2012, 55, 738–746. [CrossRef]
62. Chen, Y.; Mu, T. Thermal Stability of Ionic Liquids. In Encyclopedia of Ionic Liquids; Zhang, S., Ed.; Springer: Singapore, 2020;
pp. 1–13. ISBN 978-981-10-6739-6.
63. Parajó, J.J.; Villanueva, M.; Otero, I.; Fernández, J.; Salgado, J. Thermal Stability of Aprotic Ionic Liquids as Potential Lubricants.
Comparison with Synthetic Oil Bases. J. Chem. Thermodyn. 2018, 116, 185–196. [CrossRef]
64. Zhang, L.; Wei, L.; Zhai, S.; Zhao, D.; Sun, J.; An, Q. Hydrogen Bond Promoted Thermal Stability Enhancement of Acetate Based
Ionic Liquid. Chin. J. Chem. Eng. 2020, S1004954120300847. [CrossRef]
65. Monteiro, B.; Maria, L.; Cruz, A.; Carretas, J.M.; Marçalo, J.; Leal, J.P. Thermal Stability and Specific Heats of Coordinating Ionic
Liquids. Thermochim. Acta 2020, 684, 178482. [CrossRef]
66. Rotrekl, J.; Jandová, V.; Storch, J.; Velíšek, P.; Cuřínová, P.; Schwarz, J.; Wagner, Z.; Bendová, M. Thermal Properties of
Novel Oligoether-Substituted Ionic Liquids and the Influence of Alkyl-Substituent Isomery. Fluid Phase Equilibria 2020,
514, 112561. [CrossRef]
67. Kuhn, B.L.; Osmari, B.F.; Heinen, T.M.; Bonacorso, H.G.; Zanatta, N.; Nielsen, S.O.; Ranathunga, D.T.S.; Villetti, M.A.; Frizzo,
C.P. Dicationic Imidazolium-Based Dicarboxylate Ionic Liquids: Thermophysical Properties and Solubility. J. Mol. Liq. 2020,
308, 112983. [CrossRef]
68. Thasneema, K.K.; Thayyil, M.S.; Rosalin, T.; Elyas, K.K.; Dipin, T.; Sahu, P.K.; Krishna Kumar, N.S.; Saheer, V.C.; Messali, M.;
Hadda, T.B. Thermal and Spectroscopic Investigations on Three Phosphonium Based Ionic Liquids for Industrial and Biological
Applications. J. Mol. Liq. 2020, 307, 112960. [CrossRef]
69. Talebi, M.; Patil, R.A.; Armstrong, D.W. Physicochemical Properties of Branched-Chain Dicationic Ionic Liquids. J. Mol. Liq. 2018,
256, 247–255. [CrossRef]
70. Navarro, P.; Larriba, M.; Rojo, E.; García, J.; Rodríguez, F. Thermal Properties of Cyano-Based Ionic Liquids. J. Chem. Eng. Data
2013, 58, 2187–2193. [CrossRef]
71. Efimova, A.; Pfützner, L.; Schmidt, P. Thermal Stability and Decomposition Mechanism of 1-Ethyl-3-Methylimidazolium Halides.
Thermochim. Acta 2015, 604, 129–136. [CrossRef]
72. Eshetu, G.G.; Jeong, S.; Pandard, P.; Lecocq, A.; Marlair, G.; Passerini, S. Comprehensive Insights into the Thermal Stability,
Biodegradability, and Combustion Chemistry of Pyrrolidinium-Based Ionic Liquids. ChemSusChem 2017, 10, 3146–3159. [CrossRef]
73. Parajó, J.J.; Villanueva, M.; Troncoso, J.; Salgado, J. Thermophysical Properties of Choline and Pyridinium Based Ionic Liquids as
Advanced Materials for Energy Applications. J. Chem. Thermodyn. 2020, 141, 105947. [CrossRef]
74. Cao, Y.; Mu, T. Comprehensive Investigation on the Thermal Stability of 66 Ionic Liquids by Thermogravimetric Analysis. Ind.
Eng. Chem. Res. 2014, 53, 8651–8664. [CrossRef]
Processes 2021, 9, 337 34 of 36

75. De la Hoz, A.T.; Brauer, U.G.; Miller, K.M. Physicochemical and Thermal Properties for a Series of 1-Alkyl-4-Methyl-1,2,4-
Triazolium Bis(Trifluoromethylsulfonyl)Imide Ionic Liquids. J. Phys. Chem. B 2014, 118, 9944–9951. [CrossRef] [PubMed]
76. Lorenzo, M.; Vilas, M.; Verdía, P.; Villanueva, M.; Salgado, J.; Tojo, E. Long-Term Thermal Stabilities of Ammonium Ionic Liquids
Designed as Potential Absorbents of Ammonia. RSC Adv. 2015, 5, 41278–41284. [CrossRef]
77. Bhattacharyya, S.; Shah, F.U. Thermal Stability of Choline Based Amino Acid Ionic Liquids. J. Mol. Liq. 2018, 266, 597–602. [CrossRef]
78. Brauer, U.G.; De la Hoz, A.T.; Miller, K.M. The Effect of Counteranion on the Physicochemical and Thermal Properties of
4-Methyl-1-Propyl-1,2,4-Triazolium Ionic Liquids. J. Mol. Liq. 2015, 210, 286–292. [CrossRef]
79. Feng, W.; Lu, Y.; Chen, Y.; Lu, Y.; Yang, T. Thermal Stability of Imidazolium-Based Ionic Liquids Investigated by TG and FTIR
Techniques. J. Therm. Anal. Calorim. 2016, 125, 143–154. [CrossRef]
80. Navarro, P.; Larriba, M.; García, J.; Rodríguez, F. Thermal Stability and Specific Heats of {[Emim][DCA]+[Emim][TCM]} Mixed
Ionic Liquids. Thermochim. Acta 2014, 588, 22–27. [CrossRef]
81. Shah, F.U.; Khan, I.A.; Johansson, P. Comparing the Thermal and Electrochemical Stabilities of Two Structurally Similar Ionic
Liquids. Molecules 2020, 25, 2388. [CrossRef]
82. Zhang, J.; Song, L.; Li, K.; An, Q.; Ma, H.; Yang, L.; Wei, L. Water Addition Enhanced Thermal Stability of Alkylimidazolium
Acetate in Ionosolv Treatment of Lignin. Int. J. Biol. Macromol. 2019, 141, 1055–1064. [CrossRef] [PubMed]
83. Oster, K.; Goodrich, P.; Jacquemin, J.; Hardacre, C.; Ribeiro, A.P.C.; Elsinawi, A. A New Insight into Pure and Water-Saturated
Quaternary Phosphonium-Based Carboxylate Ionic Liquids: Density, Heat Capacity, Ionic Conductivity, Thermogravimetric
Analysis, Thermal Conductivity and Viscosity. J. Chem. Thermodyn. 2018, 121, 97–111. [CrossRef]
84. Saikat, M.S.H.; Islam, M.M.; Mollah, M.Y.A.; Susan, M.A.B.H.; Miran, M.S. Thermal and Electrochemical Properties of Protic Ionic
Liquids and Their Binary Mixtures with Water. Mater. Today Proc. 2019, 15, 498–503. [CrossRef]
85. Yamaki, N.; Shiota, K.; Izato, Y.; Hoang, D.K.; Miyake, A. Thermal Hazard Analysis of a Biomass Pretreatment Process Using
Ionic Liquids. J. Therm. Anal. Calorim. 2019, 138, 2945–2953. [CrossRef]
86. Muhammad, A. Thermal and Kinetic Analysis of Pure and Contaminated Ionic Liquid: 1-Butyl-2.3-Dimethylimidazolium
Chloride (BDMIMCl). Pol. J. Chem. Technol. 2016, 18, 122–125. [CrossRef]
87. Vyazovkin, S. Modification of the Integral Isoconversional Method to Account for Variation in the Activation Energy. J. Comput.
Chem. 2001, 22, 178–183. [CrossRef]
88. Vyazovkin, S.; Burnham, A.K.; Criado, J.M.; Pérez-Maqueda, L.A.; Popescu, C.; Sbirrazzuoli, N. ICTAC Kinetics Committee
Recommendations for Performing Kinetic Computations on Thermal Analysis Data. Thermochim. Acta 2011, 520, 1–19. [CrossRef]
89. Friedman, H.L. Kinetics of Thermal Degradation of Char-Forming Plastics from Thermogravimetry. Application to a Phenolic
Plastic. J. Polym. Sci. C Polym. Symp. 1964, 6, 183–195. [CrossRef]
90. Volli, V.; Lin, W.-C.; Krishna, G.V.S.; Bhardwaj, H.; Shu, C.-M. Oxidative Stability, Thermal Hazard Analysis, and Decomposition
Kinetics of 1-Methylimidazolium Nitrate via DSC, TGA, and GC/MS. J. Therm. Anal. Calorim. 2019, 138, 3403–3413. [CrossRef]
91. Starink, M.J. The Determination of Activation Energy from Linear Heating Rate Experiments: A Comparison of the Accuracy of
Isoconversion Methods. Thermochim. Acta 2003, 404, 163–176. [CrossRef]
92. Flynn, J.H.; Wall, L.A. General Treatment of the Thermogravimetry of Polymers. J. Res. Natl. Bur. Stand. Phys. Chem. 1966,
70A. [CrossRef]
93. Ozawa, T. A New Method of Analyzing Thermogravimetric Data. BCSJ 1965, 38, 1881–1886. [CrossRef]
94. Akahira, T.; Sunose, T. Method of Determining Activation Deterioration Constant of Electrical Insulating Materials. Res. Rep.
Chiba Inst. Technol. 1971, 16, 22–31.
95. Coats, A.W.; Redfern, J.P. Kinetic Parameters from Thermogravimetric Data. Nature 1964, 201, 68–69. [CrossRef]
96. Starink, M.J. A New Method for the Derivation of Activation Energies from Experiments Performed at Constant Heating Rate.
Thermochim. Acta 1996, 288, 97–104. [CrossRef]
97. Vyazovkin, S. A Unified Approach to Kinetic Processing of Nonisothermal Data. Int. J. Chem. Kinet. 1996, 28, 95–101. [CrossRef]
98. Vyazovkin, S.; Dollimore, D. Linear and Nonlinear Procedures in Isoconversional Computations of the Activation Energy of
Nonisothermal Reactions in Solids. J. Chem. Inf. Comput. Sci. 1996, 36, 42–45. [CrossRef]
99. Vyazovkin, S. Evaluation of Activation Energy of Thermally Stimulated Solid-State Reactions under Arbitrary Variation of
Temperature. J. Comput. Chem. 1997, 18, 393–402. [CrossRef]
100. Heym, F.; Korth, W.; Thiessen, J.; Kern, C.; Jess, A. Evaporation and Decomposition Behavior of Pure and Supported Ionic Liquids
under Thermal Stress. Chem. Ing. Tech. 2015, 87, 791–802. [CrossRef]
101. Liu, S.; Chen, Y.; Shi, Y.; Sun, H.; Zhou, Z.; Mu, T. Investigations on the Thermal Stability and Decomposition Mechanism
of an Amine-Functionalized Ionic Liquid by TGA, NMR, TG-MS Experiments and DFT Calculations. J. Mol. Liq. 2015,
206, 95–102. [CrossRef]
102. Criado, J.M.; Málek, J.; Ortega, A. Applicability of the Master Plots in Kinetic Analysis of Non-Isothermal Data. Thermochim. Acta
1989, 147, 377–385. [CrossRef]
103. Málek, J. The Kinetic Analysis of Non-Isothermal Data. Thermochim. Acta 1992, 200, 257–269. [CrossRef]
104. Thomas, E.; Vijayalakshmi, K.P.; George, B.K. Kinetic Stability of Imidazolium Cations and Ionic Liquids: A Frontier Molecular
Orbital Approach. J. Mol. Liq. 2019, 276, 721–727. [CrossRef]
105. Daily, L.A.; Miller, K.M. Correlating Structure with Thermal Properties for a Series of 1-Alkyl-4-Methyl-1,2,4-Triazolium Ionic
Liquids. J. Org. Chem. 2013, 78, 4196–4201. [CrossRef] [PubMed]
Processes 2021, 9, 337 35 of 36

106. Gusain, R.; Bakshi, P.S.; Panda, S.; Sharma, O.P.; Gardas, R.; Khatri, O.P. Physicochemical and Tribophysical Properties of
Trioctylalkylammonium Bis(Salicylato)Borate (N888n-BScB) Ionic Liquids: Effect of Alkyl Chain Length. Phys. Chem. Chem. Phys.
2017, 19, 6433–6442. [CrossRef] [PubMed]
107. Montanino, M.; Carewska, M.; Alessandrini, F.; Passerini, S.; Appetecchi, G.B. The Role of the Cation Aliphatic Side Chain Length
in Piperidinium Bis(Trifluoromethansulfonyl)Imide Ionic Liquids. Electrochim. Acta 2011, 57, 153–159. [CrossRef]
108. Özdemir, M.C.; Özgün, B. Phenyl/Alkyl-Substituted-3,5-Dimethylpyrazolium Ionic Liquids. J. Mol. Liq. 2014, 200, 129–135. [CrossRef]
109. Greeson, K.T.; Hall, N.G.; Redeker, N.D.; Marcischak, J.C.; Gilmore, L.V.; Boatz, J.A.; Le, T.C.; Alston, J.R.; Guenthner, A.J.;
Ghiassi, K.B. Synthesis and Properties of Symmetrical N,N0 -Bis(Alkyl)Imidazolium Bromotrichloroferrate(III) Paramagnetic,
Room Temperature Ionic Liquids with High Short-Term Thermal Stability. J. Mol. Liq. 2018, 265, 701–710. [CrossRef]
110. Tao, R.; Tamas, G.; Xue, L.; Simon, S.L.; Quitevis, E.L. Thermophysical Properties of Imidazolium-Based Ionic Liquids: The Effect
of Aliphatic versus Aromatic Functionality. J. Chem. Eng. Data 2014, 59, 2717–2724. [CrossRef]
111. Krasovskiy, V.G.; Chernikova, E.A.; Glukhov, L.M.; Kapustin, G.I.; Koroteev, A.A. Effect of Hydroxyl Groups in a Cation Structure
on the Properties of Ionic Liquids. Russ. J. Phys. Chem. A 2018, 92, 2379–2385. [CrossRef]
112. Ferreira, M.L.; Araujo, J.M.M.; Vega, L.F.; Llovell, F.; Pereiro, A.B. Functionalization of Fluorinated Ionic Liquids: A Combined
Experimental-Theoretical Study. J. Mol. Liq. 2020, 302, 112489. [CrossRef]
113. Xue, Z.; Zhang, Y.; Zhou, X.; Cao, Y.; Mu, T. Thermal Stabilities and Decomposition Mechanism of Amino- and Hydroxyl-
Functionalized Ionic Liquids. Thermochim. Acta 2014, 578, 59–67. [CrossRef]
114. Coadou, E.; Goodrich, P.; Neale, A.R.; Timperman, L.; Hardacre, C.; Jacquemin, J.; Anouti, M. Synthesis and Thermophysical Prop-
erties of Ether-Functionalized Sulfonium Ionic Liquids as Potential Electrolytes for Electrochemical Applications. Chemphyschem
2016, 17, 3992–4002. [CrossRef]
115. Mahrova, M.; Conte, M.; Roman, E.; Nevshupa, R. Critical Insight into Mechanochemical and Thermal Degradation of
Imidazolium-Based Ionic Liquids with Alkyl and Monomethoxypoly(Ethylene Glycol) Side Chains. J. Phys. Chem. C 2014,
118, 22544–22552. [CrossRef]
116. de Miguel, I.; Morales, E.; Herradón, B.; del Río, C.; Mann, E. Synthesis and Characterization of Oligo(Oxyethylene)-
Functionalized Thiazolium Based Room Temperature Ionic Liquids. Tetrahedron Lett. 2016, 57, 3291–3293. [CrossRef]
117. Nokami, T.; Yamashita, T.; Komura, T.; Handa, N.; Shimizu, M.; Yamaguchi, K.; Domi, Y.; Usui, H.; Sakaguchi, H.; Itoh, T. Effects
of the Ether Oxygen Atom in Alkyl Side Chains on the Physical Properties of Piperidinium Ionic Liquids. Faraday Discuss. 2017,
206, 523–534. [CrossRef] [PubMed]
118. Ngo, H.L.; LeCompte, K.; Hargens, L.; McEwen, A.B. Thermal Properties of Imidazolium Ionic Liquids. Thermochim. Acta 2000,
357, 97–102. [CrossRef]
119. Clough, M.T.; Geyer, K.; Hunt, P.A.; Mertes, J.; Welton, T. Thermal Decomposition of Carboxylate Ionic Liquids: Trends and
Mechanisms. Phys. Chem. Chem. Phys. 2013, 15, 20480–20495. [CrossRef] [PubMed]
120. Rotrekl, J.; Storch, J.; Kloužek, J.; Vrbka, P.; Husson, P.; Andresová, A.; Bendová, M.; Wagner, Z. Thermal Properties of 1-Alkyl-3-
Methylimidazolium Bis(Trifluoromethylsulfonyl)Imide Ionic Liquids with Linear, Branched and Cyclic Alkyl Substituents. Fluid
Phase Equilibria 2017, 443, 32–43. [CrossRef]
121. Gusain, R.; Khatri, O.P. Fatty Acid Ionic Liquids as Environmentally Friendly Lubricants for Low Friction and Wear. RSC Adv.
2016, 6, 3462–3469. [CrossRef]
122. Xue, Z.; Qin, L.; Jiang, J.; Mu, T.; Gao, G. Thermal, Electrochemical and Radiolytic Stabilities of Ionic Liquids. Phys. Chem. Chem.
Phys. 2018, 53. [CrossRef] [PubMed]
123. Lethesh, K.C.; Shah, S.N.; Ayodele, O.B.; Mutalib, M.I.A.; Uemura, Y. Nitrile-Functionalized Azepanium Ionic Liquids: Synthesis
Characterization and Thermophysical Properties. J. Mol. Liq. 2016, 221, 1140–1144. [CrossRef]
124. Huang, G.; Lin, W.-C.; He, P.; Pan, Y.; Shu, C.-M. Thermal Decomposition of Imidazolium-Based Ionic Liquid Binary Mixture:
Processes and Mechanisms. J. Mol. Liq. 2018, 272, 37–42. [CrossRef]
125. Clough, M.T.; Crick, C.R.; Gräsvik, J.; Hunt, P.A.; Niedermeyer, H.; Welton, T.; Whitaker, O.P. A Physicochemical Investigation of
Ionic Liquid Mixtures. Chem. Sci. 2015, 6, 1101–1114. [CrossRef]
126. Navarro, P.; Larriba, M.; García, J.; Rodríguez, F. Thermal Stability, Specific Heats, and Surface Tensions of ([Emim][DCA]+[4empy][Tf2N])
Ionic Liquid Mixtures. J. Chem. Thermodyn. 2014, 76, 152–160. [CrossRef]
127. Navarro, P.; Larriba, M.; Beigbeder, J.-B.; García, J.; Rodríguez, F. Thermal Stability and Specific Heats of {[Bpy][BF4] + [Bpy][Tf2N]}
and {[Bpy][BF4] + [4bmpy][Tf2N]} Mixed Ionic Liquid Solvents. J. Therm. Anal. Calorim. 2015, 119, 1235–1243. [CrossRef]
128. Larriba, M.; Navarro, P.; Beigbeder, J.-B.; García, J.; Rodríguez, F. Mixing and Decomposition Behavior of {[4bmpy][Tf2N]+[Emim][EtSO4]}
and {[4bmpy][Tf2N]+[Emim][TFES]} Ionic Liquid Mixtures. J. Chem. Thermodyn. 2015, 82, 58–75. [CrossRef]
129. Liu, J.; Yang, W.; Li, Z.; Ren, F.; Hao, H. Experimental Investigation of Thermo-Physical Properties of Geminal Dicationic Ionic
Compounds for Latent Thermal Energy Storage. J. Mol. Liq. 2020, 307, 112994. [CrossRef]
130. Javaherian, M.; Saghanezhad, S.J. Synthesis, Characterization and Applications of Dicationic Ionic Liquids in Organic Synthesis.
MROC 2020, 17, 450–464. [CrossRef]
131. Zaky, M.T.; Nessim, M.I.; Deyab, M.A. Synthesis of New Ionic Liquids Based on Dicationic Imidazolium and Their Anti-Corrosion
Performances. J. Mol. Liq. 2019, 290, 111230. [CrossRef]
132. Cognigni, A.; Kampichler, S.; Bica, K. Surface-Active Ionic Liquids in Catalysis: Impact of Structure and Concentration on the
Aerobic Oxidation of Octanol in Water. J. Colloid Interface Sci. 2017, 492, 136–145. [CrossRef]
Processes 2021, 9, 337 36 of 36

133. Montalbán, M.G.; Víllora, G.; Licence, P. Ecotoxicity Assessment of Dicationic versus Monocationic Ionic Liquids as a More
Environmentally Friendly Alternative. Ecotoxicol. Environ. Saf. 2018, 150, 129–135. [CrossRef]
134. Bender, C.; Kuhn, B.; Farias, C.; Ziembowicz, F.; Beck, T.; Frizzo, C. Thermal Stability and Kinetic of Decomposition of Mono- and
Dicationic Imidazolium-Based Ionic Liquids. J. Braz. Chem. Soc. 2019. [CrossRef]
135. Mezzetta, A.; Perillo, V.; Guazzelli, L.; Chiappe, C. Thermal Behavior Analysis as a Valuable Tool for Comparing Ionic Liquids of
Different Classes. J. Therm. Anal. Calorim. 2019, 138, 3335–3345. [CrossRef]
136. Shirota, H.; Mandai, T.; Fukazawa, H.; Kato, T. Comparison between Dicationic and Monocationic Ionic Liquids: Liquid Density,
Thermal Properties, Surface Tension, and Shear Viscosity. J. Chem. Eng. Data 2011, 56, 2453–2459. [CrossRef]
137. Fareghi-Alamdari, R.; Hatefipour, R. Low Viscosity Azide-Containing Mono and Dicationic Ionic Liquids with Unsaturated Side
Chain. J. Mol. Liq. 2017, 225, 793–799. [CrossRef]
138. Payagala, T.; Huang, J.; Breitbach, Z.S.; Sharma, P.S.; Armstrong, D.W. Unsymmetrical Dicationic Ionic Liquids: Manipulation of
Physicochemical Properties Using Specific Structural Architectures. Chem. Mater. 2007, 19, 5848–5850. [CrossRef]
139. Zhang, H.; Li, M.; Yang, B. Design, Synthesis, and Analysis of Thermophysical Properties for Imidazolium-Based Geminal
Dicationic Ionic Liquids. J. Phys. Chem. C 2018, 122, 2467–2474. [CrossRef]
140. Boumediene, M.; Haddad, B.; Paolone, A.; Drai, M.; Villemin, D.; Rahmouni, M.; Bresson, S.; Abbas, O. Synthesis, Thermal
Stability, Vibrational Spectra and Conformational Studies of Novel Dicationic Meta-Xylyl Linked Bis-1-Methylimidazolium Ionic
Liquids. J. Mol. Struct. 2019, 1186, 68–79. [CrossRef]
141. Clarke, C.J.; Bui-Le, L.; Hallett, J.P.; Licence, P. Thermally-Stable Imidazolium Dicationic Ionic Liquids with Pyridine Functional
Groups. ACS Sustain. Chem. Eng. 2020, 8, 8762–8772. [CrossRef]
142. Krasovskiy, V.G.; Kapustin, G.I.; Gorbatsevich, O.B.; Glukhov, L.M.; Chernikova, E.A.; Koroteev, A.A.; Kustov, L.M. Properties of
Dicationic Disiloxane Ionic Liquids. Molecules 2020, 25, 2949. [CrossRef] [PubMed]