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Research Article
ChemistrySelect doi.org/10.1002/slct.202201799
Dicationic Imizadolium-Based Tetrafluoroborate Ionic
Liquids: Synthesis and Hydrothermal Stability Study
Chenqian Xu and Zhenmin Cheng*[a]
Six novel dicationic imizadolium-based tetrafluoroborate ionic
liquids were synthesized, with four of which contained hydroxyl
groups. Their chemical structures were identified by FTIR and
1
H NMR, and their onset decomposition temperatures (Tonset)
were measured by thermogravimetric analysis (TGA). For
investigating the hydrothermal stability, all DILs were mixed
with water and heated for 1, 5, and 9 hours to 240 °C in an
Introduction
Ionic liquids (ILs) are the salts completely composed of organic
cations and organic or inorganic anions, which is liquid at room
temperature or close to room temperature, also known as low
temperature molten salts.[1] Due to the myriad ion combina-
tions and the tunability of structure, ILs have been described as
“designer solvents”.[2] Advantages attributed to ILs include non-
volatility, non-flammability, high thermal and chemical stability,
and good extraction capability.[3] As a result of these features,
ILs are used for a wide range of high-temperature applications
such high-temperature lubricants,[4] solvents for high-temper-
ature organic reactions,[5] heat-transfer fluids,[6] and thermal
energy storage.[7] To develop ILs with superior thermal stability,
dicationic ILs (DILs) are recommended, whose excellent thermal
stability is ascribed to higher charges, greater molecular
weight, and stronger intermolecular interactions of DILs.[8]
In order to quantitatively evaluate the heat resistance 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 in a
selected time y) respectively. Although many studies have
indicated that Tonset obtained by dynamic TGA overestimates
the thermal stability,[9] it is still widely used to express the
stability of ILs from divergent papers.[10] Tonset and Tz/y are
imprecise to predict whether ILs are stable enough in long-
term runnings at high temperature, because the heating rates,
gas atmosphere, and existence of impurities all influence the
results of TGA.[11] Some ILs whose Tonset all surpass 400 °C are
heated for 15 weeks to 200 °C in an oxidizing environment,
then, unexpectedly, all of them had completely polymerized or
[a] C. Xu, Prof. Z. Cheng
State Key Laboratory of Chemical Engineering
School of Chemical Engineering
East China University of Science and Technology
Shanghai 200237, PR China
E-mail: zmcheng@ecust.edu.cn
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/slct.202201799
ChemistrySelect 2022, 7, e202201799 (1 of 8)
www.chemistryselect.org
airtight kettle.The results show that DILs with hydroxyls have a
higher Tonset but they exhibit evident changes in chemical
structures after heating with water for 9 hours. The conflicts
between Tonset and long-term stability tests is ascribed to the
reason that water forms new hydrogen bonds with hydroxyls
and therefore weakens the intramolecular interaction between
the cation and anion.
solidified.[12] Besides, [BMIM][NTf2], which is generally consid-
ered to be thermally stable, was completely reduced to ash
after heated to 300 °C for only 96 hours in air.[12] Therefore, it is
necessary to study the long-term thermal stability of ILs in a
practical surroundings.
The existence of water alters the thermal stability of ILs,[13]
however, mixing with water is almost inevitable to avoid when
ILs is used as solvents, catalyst, absorbents, and heat transfer
fluids.[13a,14] The long-term thermal stability of ILs in dry
atmosphere has been studied, but there are few studies on the
long-term hydrothermal stability. The purpose of this work is to
find water-resistant DILs with great thermal stability, so as to
broaden the application of DILs. Six DILs with imidazolium
cation and [BF4] anion were synthesized and determined by
FTIR and NMR, and their thermal stability was investigated by
TGA. Our previous study has proved that hydrophilic ionic
liquids can be used as an inert solvent for three-phase
methanol synthesis.[14a] In this reaction, the optimum temper-
ature is about 240 °C, and water, is produced due to reaction
between CO2 and H2 so the long-term hydrothermal stability of
DILs was studied under 240 °C and 3 MPa, which is close to the
conditions of methanol synthesis. BF4 is chosen as the anion
because it not only has better hydrophilicity than NTF2- and
PF6 , but also has excellent water resistance and thermal
stability.[15] The long-term hydrothermal stability of different
DILs were obtained by comparing the FTIR spectra, so as to
explore their long-term dependability in the presence of a large
amount of water.
Results and Discussion
Structural Characterization of precursors and DILs
The structures of the DILs characterized by NMR and FTIR are in
good agreement with forecast, so it can be concluded that the
process of synthesis reported in second section are practicable.
Due to the strong electronegativity of [Br] , the precursors of
the six DILs have obvious hydrogen bond peaks in Figure S3.
As can be seen from c) and e), the peak of hydrogen bond in
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DILs without hydroxyl disappears, indicating that [BF4] has

weak ability to form hydrogen bonds with H2 (the proton in the
carbon atom between two nitrogen atoms in the imidazolium
ring).
For the imidazolium DILs, the 1H NMR chemical shifts of H2
are related to the hydrogen bond interaction between the
anions and H2, and the large downfield shift means the
hydrogen bond interaction is strong.[16] As shown in Table 1,
the decrease of chemical shifts of H2 of [C8(C2IM)2] + and [C10
(C2IM)2] + DILs is recognizable after changing the anions from
[Br] to [BF4] . This disparity indicates that there are stronger
hydrogen bonds between cation and [Br] than those between
cation and [BF4] . However, the H2 signals show marked
changes in chemical shifts to higher fields after adding
hydroxyl to the cationic heads of [C8(C2IM)2][Br]2 and
[C10(C2IM)2][Br]2, which indicates that the interaction between
anions and H2 is inhibited. The reason of this inhibitation is
attributed to the preferentially formed hydrogen bonds
between anions and hydroxyl groups. Similarly, the H2 signals
of [C8(C2OHIM)2] + and [C10(C2OHIM)2] + DILs slightly diverge
before and after changing the anion, which also proves that
hydroxyl groups have an inhibitory effect on the formation of
hydrogen bonds between H2 and anions. Besides, the chemical
shifts of H2 of [C3(C1OH)2(C2IM)2] + DILs barely alter whether
changing its anion or introducing hydroxyl into its cationic
heads. It is ascribed to the interaction between anions and
hydroxyl groups on the branched chain.

Thermal stability
The thermal stability of six DILs is determined by TGA, and the
corresponding thermal decomposition curves are in Figure 1.
The specific pyrolysis temperatures of each DILs obtained from
TGA are collected in Table 2. Tonset, which is basically known as
the short-term thermal stability, is defined as the intersection
of the baseline of zero weight loss and the tangent of the
Figure 1. a) TGA and b) DTG curves of DILs at a heating rate of 10 °C/min in
nitrogen atmosphere.
weight versus temperature curve as decomposition occurs.[10a]
And Tz (decomposition degree z) is also a parameter to
characterize the short-term thermal stability, which directly

Table 1. 1H NMR chemical shifts δ (ppm) of precursors and DILs.

Precursors H2 DILs H2 Δδ

[C3(C1OH)2(C2IM)2][Br]2 9.25 [C3(C1OH)2(C2IM)2][BF4]2 9.15 0.1

[C3(C1OH)2(C2OHIM)2][Br]2 9.15 [C3(C1OH)2(C2OHIM)2][BF4]2 9.02 0.13
[C8(C2IM)2][Br]2 9.50 [C8(C2IM)2][BF4]2 9.17 0.33
[C8(C2OHIM)2][Br]2 9.27 [C8(C2OHIM)2][BF4]2 9.15 0.12
[C10(C2IM)2][Br]2 9.53 [C10(C2IM)2][BF4]2 9.18 0.35
[C10(C2OHIM)2][Br]2 9.28 [C10(C2OHIM)2][BF4]2 9.13 0.15

Table 2. Thermal decomposition temperature of DILs synthesized in this paper.

Entry DILs T10%/°C Tonset/°C Tpeak/°C

1 [C3(C1OH)2(C2IM)2][BF4]2 331 356 398

2 [C3(C1OH)2(C2OHIM)2][BF4]2 320 355 376
3 [C8(C2IM)2][BF4]2 316 Step 1: 304 448
Step 2: 383
4 [C8(C2OHIM)2][BF4]2 342 343 369
5 [C10(C2IM)2][BF4]2 306 Step 1: 287 450
Step 2: 393
6 [C10(C2OHIM)2][BF4]2 313 324 335

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Research Article
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Table 3. Observations of Physical Changes in DILs after the long-term thermal stability experiments.

Treatment means [C3(C1OH)2(C2IM)2] [C3(C1OH)2(C2OHIM)2] [C8(C2IM)2] [C8(C2OHIM)2] [C10(C2IM)2] [C10(C2OHIM)2]

[BF4]2 [BF4]2 [BF4]2 [BF4]2 [BF4]2 [BF4]2

neat semitransparent semitransparent colorless light colorless light

white solid white solid liquid yellow liquid yellow
liquid liquid
heating 1 h light brown light brown dark dark dark dark brown
with water liquid, viscous liquid, very brown brown brown liquid,
viscous liquid, liquid, liquid, slightly
slightly slightly slightly viscous viscous
viscous viscous
heating 5 h dark brown dark brown dark dark dark dark brown
with water solid, sticky solid, sticky brown brown brown liquid,
liquid, liquid, liquid, slightly
slightly slightly slightly viscous
viscous viscous viscous
heating 9 h dark brown dark brown dark orange dark orange
with water solid, sticky solid, sticky brown solid, brown solid,
liquid, very sticky liquid, slightly
slightly slightly sticky
viscous viscous
heating 9 h dark brown dark brown dark dark dark dark brown
without water powder powder brown brown brown liquid, very
liquid, liquid, liquid, viscous
slightly slightly slightly
viscous viscous viscous

Figure 2. The comparison of DILs before and after the long-term thermal stability experiments under different conditions.

shows the temperatures at different decomposition degrees.[17]
Besides, thermal stability is also characterized by the temper-
ature of maximum degradation (Tpeak).[18] As show in Table 2,
the introduction of hydroxyl groups into the cationic heads of
[C3(C1OH)2(C2IM)2][BF4]2 decreases its T10%, Tonset, and Tpeak in
varying degrees. It is generally believed that hydroxyl groups
will reduce the thermal stability of ILs,[19] which is attributed to
the higher chemical activity and easier decomposition of the
hydroxyl groups.[20] But the decomposition temperatures of
[C8(C2IM)2][BF4]2 and [C10(C2IM)2][BF4]2 are lower than those of
[C8(C2OHIM)2][BF4]2 and [C10(C2OHIM)2][BF4]2 respectively. In
particular, the introduction of hydroxyl groups into
[C8(C2IM)2][BF4]2 significantly improves the T10%, Tonset, and Tpeak
by 26 °C, 39 °C and 33 °C. The reason why [C8(C2OHIM)2][BF4]2
and [C10(C2OHIM)2][BF4]2 are more stable is that the strong
hydrogen bonding blocks thermal decomposition reaction to
some extent.[20] Hydrogen bonding increases the decomposi-
tion temperature of DILs with longer linkage chain, while for

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Figure 3. FTIR spectra of [C3(C1OH)2(C2IM)2][BF4]2 before and after heated with
water at 240 °C.
Figure 4. FTIR spectra of [C3(C1OH)2(C2OHIM)2][BF4]2 before and after heated
with water at 240 °C.
DILs with shorter linkage chain, hydrogen bonding has a
negative impact on thermal stability because of its high
activity.
In addition, it is obvious that the pyrolysis processes of
[C8(C2IM)2][BF4]2 and [C10(C2IM)2][BF4]2 are divided into two
stages, as shown in both TGA and DTG curves in Figure 1.
These processes are ascribed to the stepwise decomposition of
cation and anion of DILs at different temperatures.[18a,21] After
introducing hydroxyl into the cationic heads, the TGA curves
show that the pyrolysis of [C8(C2OHIM)2][BF4]2 and
[C10(C2OHIM)2][BF4]2 are one-step processes, which can be
attributed to the fact that the hydroxyl strengthens the
intramolecular interaction between cation and anion, and there
is more energy in the chemical bond.[8a,22] In addition to
functional groups, the length of the linkage chain of DILs also
has a remarkable effect on the thermal stability. Table 2 reveals
that the Tonset of [C3(C1OH)2(C2IM)2][BF4]2 and
[C3(C1OH)2(C2OHIM)2][BF4]2 is higher than that of DILs with the
C8 and C10 linkage chain. Therefore, the thermal stability
decreases with the increase of the linkage chain length of
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DILs,just like the length of the alkyl side chain has a negative
effect on the thermal stability of conventional ILs.[23]
Effect of water on the long-term thermal stability of DILs
Many previous studies have proved that water has different
effects on the thermal stability of different ILs. On one hand,
water hinders the degradation reaction of [C2MIM][Ac] and
[C4MIM][Ac], as shown by Williams et al..[9a] This result is in line
with the research of [C2MIM][AcO] and [C4MIM][AcO].[24] On the
other hand, Tonset of the quaternary phosphonium carboxylate
ILs decreases by 19.8 °C at most when the water content is
saturated.[13a] Besides, the TGA curves of two protic ILs,
[DEMA][HSO4] and [DEMA][CF3COO], decrease markedly with
the increase of water content.[13b] In previous studies, the
difference of thermal decomposition temperatures between
pure ILs and mixtures with water determined by TGA is the
main evidence to prove the effect of water on the thermal
stability. Although it is general and convenient to analyze
thermal properties by TGA, water will inevitably evaporate and
be taken away by protective gas as the system heats up. ILs
have excellent thermal stability, and the decomposition
temperatures can reach 200 or even 300 °C, which means that
there is hardly any water in the experimental environment
when ILs really start to decompose. As a result, another method
is developed to study the long-term hydrothermal stability.
Approximately 0.1 g of each DIL was mixed with 10 g water in
an airtight reaction kettle. Then the air in the kettle was
displaced with dry nitrogen, and the kettle was heated to
240 °C for 1, 5, and 9 hours respectively. The pressure of water
vapor in the kettle is 3 MPa. After heating, dry samples were
obtained by rotary evaporation and vacuum drying. Neat DILs
were also heated to 240 °C for 9 hours under dry nitrogen
atmosphere as a comparison.
Physical Observations
Physical observations of the DILs throughout the long-term
thermal stability experiments with or without water are
summarized in Table 3, and photos demonstrating the DILs
heated under different conditions are presented in Figure 2. All
of the DILs exhibit an evident change in color after exposure to
the high temperature environment with or without water. The
cause of this change in color is still unknown. The DILs without
hydroxyl ([C8(C2IM)2][BF4]2 and [C10(C2IM)2][BF4]2) remained fluid
after heating, so they were the most resistant to degradation
under all of the treatment means on the basis of physical
appearance. [(C1OH)2(C2IM)2][BF4]2 and
[C3(C1OH)2(C2OHIM)2][BF4]2 became fluid after heating with
water for 1 hour, but both of them turned back to sticky solid
after 5 and 9 hours and turned into dark brown powder after
heating in an anhydrous surroundings for 9 hours, which infers
that the physical appearance after heating is greatly affected
by moisture and heating time in the environment. By
comparing the appearance of [C8(C2OHIM)2][BF4]2 and
[C10(C2OHIM)2][BF4]2 heated with water for 1, 5, and 9 hours
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Research Article
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Figure 5. FTIR spectra of six DILs heated with and without water to 240 °C for 9 hours.

Figure 6. FTIR spectra of [C8(C2IM)2][BF4]2 before and after heated with water Figure 7. FTIR spectra of [C8(C2OHIM)2][BF4]2 before and after heated with
to 240 °C. water to 240 °C.

respectively, it is discovered that the color of the samples
turned orange significantly after heating for 9 hours.
Chemical Changes
FTIR was completed on the DILs after the heating process in
attempts to determine chemical changes that were occurring
in the DILs and correlate them to the long-term thermal
stability under the hydrothermal environment. There are no
significant changes in the FTIR spectra
[C3(C1OH)2(C2IM)2][BF4]2 and [C3(C1OH)2(C2OHIM)2][BF4]2 over the
heating procedure. They are represented in Figure 3 and
Figure 4, respectively. The figures show the tansmittance of the
neat DILs and the DILs heated with water in 1, 5, and 9 hours at
240 °C. One little change is that the double peak at 3500 cm 1
for neat [C3(C1OH)2(C2IM)2][BF4]2 become single peak after
heating, which is representative of hydroxyl. Both of Figure 3
and Figure 4 show a decrease in intensity of the weak peak at
about 3500 cm 1 representing hydroxyl groups, which supports
that hydroxyl is more sensitive to temperature and water than
other parts of DILs. As shown in Figure 4, the stretching
of vibration peaks of C O at 1057 and 1000 cm 1 decrease after
heating, and the stretching vibration peak of B F which is
previously covered appears because of the better stability of

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Figure 8. FTIR spectra of [C10(C2IM)2][BF4]2 before and after heated with water
to 240 °C.
Figure 9. FTIR spectra of [C10(C2OHIM)2][BF4]2 before and after heated with
water to 240 °C.
anion. These chemical observations are supported by the
thermal decomposition temperatures of
[C3(C1OH)2(C2OHIM)2][BF4]2 are lower than
[C3(C1OH)2(C2IM)2][BF4]2. After 9 hours heating, one more minor
change is a decrease in intensity of the weak peaks at 2989 and
2894 cm 1 for [C3(C1OH)2(C2IM)2][BF4]2, attributed to the methyl
groups, which is due to the breakdown of DILs with the non-
nucleophilic [BF4] anion is proposed to proceed via an SN1
mechanism to give the neutral imidazole and a substituted
alkyl carbocation.[25] The FTIR spectra of
[C3(C1OH)2(C2OHIM)2][BF4]2 and [C3(C1OH)2(C2IM)2][BF4]2 in Fig-
ure 5 a) and b) show great consistency between the samples
heating with water and those heating without water, which
means the water cannot promote the structural changes, but
only affect their physical appearance after heating.
The FTIR spectra of [C8(C2IM)2][BF4]2 remains unchanged
throughout 9 hours heating process, as shown in Figure 6. The
results of spectra are as stable as its physical appearance in
long-term hydrothermal stability experiments described in
Table 3. Compared with the analogical DIL, the structure of
[C8(C2OHIM)2][BF4]2 displays many distinct changes in Figure 7
that mirror the physical observations previously described in
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Table 3. The significant decreases are seen in the transmittance
at 3674, 2902, 2996, and 1399 cm 1. During the heating
process, there is a new cluster of peak at 3674 cm 1, ascribed
to the destruction of hydrogen bonding between cation and
anion. This
new peak is the left shift and sharpness of the hydroxyl
peak of stretching vibration, and the enhancement of hydroxyl
O H bending vibration at 1399 cm 1 is also affected by the
weakening of hydrogen bonding. The peaks at 2996 and
2902 cm 1 are regarded as the forward movement of meth-
ylene peaks at 2933 and 2860 cm 1. The methyl peaks are from
the fracture of linkage chain, because the thermolysis of ionic
liquids with [BF4] is more likely to occur at the longer alkyl
chain side.[26]
The peaks of FTIR spectra for [C10(C2IM)2][BF4]2 before and
after heating with water for 9 hours in Figure 8 remain
immobile, and both of the chemical spectra and physical
appearance prove its excellent thermal stability in hydro-
thermal environment. However, [C10(C2OHIM)2][BF4]2 exhibits
many changes during the heating process in Figure 9, just like
[C8(C2OHIM)2][BF4]2.
There are some changes in the FTIR spectra of four hydroxyl
containing DILs after the long-term thermal stability experi-
ments in hydrothermal environment, especially for
[C8(C2OHIM)2][BF4]2 and [C10(C2OHIM)2][BF4]2, while these DILs
are heat-resistant according to TGA results. In other words, the
long-term hydrothermal stability of [C8(C2OHIM)2][BF4]2 and
[C10(C2OHIM)2][BF4]2 is far from consistent with their short-term
stability from TGA. On the contrary, [C8(C2IM)2][BF4]2 and
[C10(C2IM)2][BF4]2 show extraordinary hydrothermal stability,
whose FTIR spectra before and after baking in different
conditions are completely consistent, while their Tonset are lower
than the remaining DILs. Besides, there is no evident structural
changes of the six DILs after baking under the protection of dry
nitrogen at 240 °C for 9 hours, as shown in Figure 5, indicating
that hydrothermal surroundings accelerates the thermal de-
composition of DILs containing hydroxy. The degradation of
DILs with [BF4] most probably gives rise to the formation of
alkylimidazole, alkyl fluoride and boron trifluoride. In particular,
the formation of alcohol and hydrogen fluorideis is possible
when water is present.[27] The hydrogen fluorideis and water
form new hydrogen bonds with hydroxyl groups, which
weakens the interaction between cation and anion and results
in the decrease of thermal stability of hydroxyl containing
DILs.[23b,28] This relationship between hydrogen bonding and
thermal stability explains that [C8(C2OHIM)2][BF4]2 and
[C10(C2OHIM)2][BF4]2 tend to break down in the high temper-
ature environment containing water, and [C8(C2IM)2][BF4]2 and
[C10(C2IM)2][BF4]2 tend to be steady under same conditions.
Therefore, the decomposition temperatures from TGA are
slightly referential for the real industrial runnings, and the
stimulation of actual surroundings needs to be pay more
attention in the future investigations of thermal stability so
that the long-term thermal properties of DILs can be reliable.
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Research Article
ChemistrySelect doi.org/10.1002/slct.202201799
Conclusion
Six novel imizadolium DILs with [BF4] were synthesized and
tested for short-term thermal stability in TGA and for long-term
hydrothermal stability at 240 °C in an airtight reaction kettle.
The introduction of hydroxyl groups makes the decomposition
temperatures of [C8(C2IM)2][BF4]2 and [C10(C2IM)2][BF4]2 higher
and transforms both of them from two-step decomposition to
one-step. Those changes are due to the hydrogen bonding
between the hydroxyl groups and anions.
In the long-term hydrothermal stability tests,
[C8(C2IM)2][BF4]2 and [C10(C2IM)2][BF4]2, whose Tonset are lower
than the other DILs, were the most stable in high temperature
environment containing water according to both of physical
observations and FTIR spectra. The colors of [C8(C2OHIM)2][BF4]2
and [C10(C2OHIM)2][BF4]2 heated with water for 9 hours are
orange and different from the dark brown samples obtained
after heating for 1 and 5 hours. Correspondingly, their FTIR
spectra changed dramatically after heating for 9 hours with
water. So the long-term hydrothermal resistance of
[C8(C2OHIM)2][BF4]2 and [C10(C2OHIM)2][BF4]2 contradicts the
results from TGA. [C3(C1OH)2(C2IM)2][BF4]2 and
[C3(C1OH)2(C2OHIM)2][BF4]2 show a minor alteration in both of
physical and chemical observations. By comparing the structure
of DILs after long-term heating in the presence or absence of
water, it can be concluded that water accelerates the pyrolysis
of DILs with hydroxyl groups and stronger hydrogen bonds
make DILs easier to decompose. Therefore, it is necessary for
the future investigations of thermal stability of DILs to simulate
real environment to make the long-term stability reliable and
precise.
Experimental Section
Characterization of chemical structure
The DILs were characterized by 1H NMR and Fourier transform
infrared (FTIR). 1H NMR spectra were recorded in DMSO-d6 on a
Bruker Avance 600 spectrometer using tetramethylsilane (TMS) as
an internal standard. The NMR results were analyzed and processed
by MestReNova. The structure was determined by judging the
position and integration of the peak in the NMR spectrum. FTIR
spectra were recorded on a Nicolet iS20 spectrophotometer with
Attenuated Total Reflection (ATR) accessory. Scans were repeated
32 times at a resolution of 4 cm 1 and OMNIC was used to analyze
the scanning data. By combining FTIR and 1H NMR spectra, the
structure of DILs synthesized in the experiment is determined.
Thermal analysis
In order to quantitatively evaluate the thermal stability of DILs, T10%,
Tonset, and Tpeak were obtained by thermogravimetric analysis (TGA)
in an alumina pan using Netzsch STA 449 F3. Mass sensitivity is
0.1 μg, and the temperature fluctuation is less than � 0.3 °C.
Around 20 mg of sample was heated with the ramp of 10 °C/min
from room temperature to 800 °C and the N2 flow rate was 60 mL/
min.
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Long-term hydrothermal stability tests
About 0.1 g DILs and 10 g water were added to a reaction kettle
with good air tightness. First, the air was discharged with nitrogen,
and the kettle was heated to 240 °C for 1, 5, and 9 hours. The
pressure in the kettle was 3 MPa. Then, samples were obtained by
rotating evaporation and vacuum drying. As control groups, pure
DILs were also kept at 240 °C for 9 hours under the protection of
nitrogen. By comparing the FTIR results of DILs after different
heating conditions, the long-term hydrothermal stability can be
determined.
Supporting Information Summary
Supporting information includes the experimental section with
detailed procedure to synthesize DILs as well as analysis
methods.
Acknowledgements
The authors are grateful to the financial supports from and the
National Key R&D Program of China (No. 2019YFC1906705) and
the National Natural Science Foundation of China (No.
21676085).
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
Research data are not shared.
Keywords: hydroxyl · hydrogen bonds · hydrothermal
stability · ionic liquids · water
[1] a) K. S. Egorova, V. P. Ananikov, J. Mol. Liq. 2018, 272, 271–300; b) Y.
Qiao, W. Ma, N. Theyssen, C. Chen, Z. Hou, Chem. Rev. 2017, 117, 6881–
6928; c) R. D. Rogers, K. R. Seddon, Science 2003, 302, 792–793; d) T.
Welton, Chem. Rev. 1999, 99, 2071–2084.
[2] a) A. Boruń, J. Mol. Liq. 2019, 276, 214–224; b) S. Jiang, Y. Hu, Y. Wang, X.
Wang, J. Phys. Chem. Ref. Data 2019, 48, 033101.
[3] a) M. Götz, R. Reimert, S. Bajohr, H. Schnetzer, J. Wimberg, T. J. S.
Schubert, Thermochim. Acta 2015, 600, 82–88; b) M. Amde, J.-F. Liu, L.
Pang, Environ. Sci. Technol. 2015, 49, 12611–12627; c) K. Ghandi, Green
Sustainable Chem. 2014, 4, 44–53.
[4] a) G. Huang, Q. Yu, M. Cai, F. Zhou, W. Liu, Tribol. Int. 2017, 114, 65–76;
b) J. Lee, C. D. Yeo, Z. Hu, V. D. Thalangama-Arachchige, J. Kaur, E. L.
Quitevis, G. Kumar, Y. P. Koh, S. Simon, Metals 2019, 9, 1180; c) Y. Li, S.
Zhang, Q. Ding, D. Feng, B. Qin, L. Hu, Tribol. Int. 2017, 114, 121–131.
[5] N. Kaur, Synth. Commun. 2018, 48, 1588–1613.
[6] a) J. Liu, F. Wang, L. Zhang, X. Fang, Z. Zhang, Renewable Energy 2014,
63, 519–523; b) W. Wang, Z. Wu, B. Li, B. Sundén, J. Therm. Anal. Calorim.
2019, 136, 1037–1051.
[7] a) A. Lamas, I. Brito, F. Salazar, T. A. Graber, J. Mol. Liq. 2016, 224, 999–
1007; b) A. Mehrkesh, A. T. Karunanithi, Comput. Chem. Eng. 2016, 93,
402–412.
[8] a) J. Liu, W. Yang, Z. Li, F. Ren, H. Hao, J. Mol. Liq. 2020, 307, 112994;
b) H. Shirota, T. Mandai, H. Fukazawa, T. Kato, J. Chem. Eng. Data 2011,
56, 2453–2459; c) J. L. Anderson, R. Ding, A. Ellern, D. W. Armstrong, J.
Am. Chem. Soc. 2005, 127, 593–604.
[9] a) M. L. Williams, S. P. Holahan, M. E. McCorkill, J. S. Dickmann, E. Kiran,
Thermochim. Acta 2018, 669, 126–139; b) J. J. Parajó, T. Teijeira, J.
© 2022 Wiley-VCH GmbH

Research Article
ChemistrySelect doi.org/10.1002/slct.202201799
Fernández, J. Salgado, M. Villanueva, J. Chem. Thermodyn. 2017, 112,
105–113; c) A. Efimova, J. Varga, G. Matuschek, M. R. Saraji-Bozorgzad, T.
Denner, R. Zimmermann, P. Schmidt, J. Phys. Chem. B 2018, 122, 8738–
8749; d) A. M. Dunaev, V. B. Motalov, L. S. Kudin, Entropy 2021, 23, 1478;
e) V. Volpe, B. Brunetti, G. Gigli, A. Lapi, S. Vecchio Ciprioti, A. Ciccioli, J.
Phys. Chem. B 2017, 121, 10382–10393.
[10] a) C. Maton, N. D. Vos, C. V. Stevens, Chem. Soc. Rev. 2013, 42, 5963–
5977; b) W. Al-Sallami, P. Parsaeian, A. Neville, Lubr. Sci. 2019, 31, 229–
238.
[11] C. Xu, Z. Cheng, Processes 2021, 9, 337.
[12] E. B. Fox, L. T. Smith, T. K. Williamson, S. E. Kendrick, Energy Fuels 2013,
27, 6355–6361.
[13] a) K. Oster, P. Goodrich, J. Jacquemin, C. Hardacre, A. P. C. Ribeiro, A.
Elsinawi, J. Chem. Thermodyn. 2018, 121, 97–111; b) M. S. H. Saikat, M. M.
Islam, M. Y. A. Mollah, M. A. B. H. Susan, M. S. Miran, Mater. Today: Proc.
2019, 15, 498–503.
[14] a) D. Ling, P. Liu, Z. Cheng, AIChE J. 2017, 63, 226–237; b) F. Giacalone,
M. Gruttadauria, ChemCatChem 2016, 8, 664–684; c) W. Zhang, L. Ye, J.
Jiang, J. Environ. Chem. Eng. 2015, 3, 227–232.
[15] a) J. G. Huddleston, A. E. Visser, W. M. Reichert, H. D. Willauer, G. A.
Broker, R. D. Rogers, Green Chem. 2001, 3, 156–164; b) J. D. Holbrey, K. R.
Seddon, J. Chem. Soc. Dalton Trans. 1999, 13, 2133–2140; c) A. E. Visser,
R. P. Swatloski, W. M. Reichert, S. T. Griffin, R. D. Rogers, Ind. Eng. Chem.
Res. 2000, 39, 3596–3604.
[16] a) G. Avent, P. A. Chaloner, M. P. Day, K. R. Seddon, T. Welton, J. Chem.
Soc. Dalton Trans. 1994, 23, 3405–3413.
[17] a) J. J. Parajó, M. Villanueva, I. Otero, J. Fernández, J. Salgado, J. Chem.
Thermodyn. 2018, 116, 185–196; b) B. L. Kuhn, B. F. Osmari, T. M. Heinen,
H. G. Bonacorso, N. Zanatta, S. O. Nielsen, D. T. S. Ranathunga, M. A.
Villetti, C. P. Frizzo, J. Mol. Liq. 2020, 308, 112983; c) K. K. Thasneema,
M. S. Thayyil, T. Rosalin, K. K. Elyas, T. Dipin, P. K. Sahu, N. S.
Krishna Kumar, V. C. Saheer, M. Messali, T. B. Hadda, J. Mol. Liq. 2020,
307, 112960; d) Z. Huang, X. Wang, T. Lu, D. Nong, J. Zhao, M. Wei, L.
Teng, J. Therm. Anal. Calorim. 2019, 140, 695–712; e) M. Talebi, R. A. Patil,
D. W. Armstrong, J. Mol. Liq. 2018, 256, 247–255.
ChemistrySelect 2022, 7, e202201799 (8 of 8)
23656549, 2022, 32, Downloaded from https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/slct.202201799 by University Of Texas - Dallas, Wiley Online Library on [18/02/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
[18] a) L. Zhang, L. Wei, S. Zhai, D. Zhao, J. Sun, Q. An, Chin. J. Chem. Eng.
2020, 5,1293–1301; b) M. Soltani, B. Siu, E. A. Salter, A. Wierzbicki, K. N.
West, J. H. Davis, Tetrahedron Lett. 2017, 58, 4628–4631; c) A. Efimova, L.
Pfützner, P. Schmidt, Thermochim. Acta 2015, 604, 129–136; d) G. G.
Eshetu, S. Jeong, P. Pandard, A. Lecocq, G. Marlair, S. Passerini,
ChemSusChem 2017, 10, 3146–3159; e) J. J. Parajó, M. Villanueva, J.
Troncoso, J. Salgado, J. Chem. Thermodyn. 2020, 141, 105947.
[19] a) Y. Cao, T. Mu, Ind. Eng. Chem. Res. 2014, 53, 8651–8664; b) M. L.
Ferreira, J. M. M. Araujo, L. F. Vega, F. Llovell, A. B. Pereiro, J. Mol. Liq.
2020, 302, 112489.
[20] Y. Song, Y. Xia, Z. Liu, Tribol. Trans. 2012, 55, 738–746.
[21] Z. Ullah, M. A. Bustam, Z. Man, A. S. Khan, Procedia Eng. 2016, 148, 215–
222.
[22] a) H. Zhang, J. Liu, M. Li, B. Yang, J. Mol. Liq. 2018, 269, 738–745; b) F.
Deng, Z. K. Reeder, K. M. Miller, J. Phys. Org. Chem. 2014, 27, 2–9.
[23] a) E. Coadou, P. Goodrich, A. R. Neale, L. Timperman, C. Hardacre, J.
Jacquemin, M. Anouti, ChemPhysChem 2016, 17, 3992–4002; b) M.
Mahrova, M. Conte, E. Roman, R. Nevshupa, J. Phys. Chem. C 2014, 118,
22544–22552; c) I. de Miguel, E. Morales, B. Herradón, C. del Río, E.
Mann, Tetrahedron Lett. 2016, 57, 3291–3293; d) J. Rotrekl, V. Jandová, J.
Storch, P. Velíšek, P. Cuřínová, J. Schwarz, Z. Wagner, M. Bendová, Fluid
Phase Equilib. 2020, 514, 112561.
[24] J. Zhang, L. Song, K. Li, Q. An, H. Ma, L. Yang, L. Wei, Int. J. Biol.
Macromol. 2019, 141, 1055–1064.
[25] T. Erdmenger, J. Vitz, F. Wiesbrock, U. S. Schubert, J. Mater. Chem. 2008,
18, 5267–5273.
[26] H. Ohtani, S. Ishimura, M. Kumai, Anal. Sci. 2008, 24, 1335–1340.
[27] M. C. Kroon, W. Buijs, C. J. Peters, G. J. Witkamp, Thermochim. Acta 2007,
465, 40–47.
[28] a) Z. Zhang, A. A. M. Salih, M. Li, B. Yang, Energy Fuels 2014, 28, 2802–
2810; b) L. Cammarata, S. G. Kazarian, P. A. Salter, T. Welton, Phys. Chem.
Chem. Phys. 2001, 3, 5192–5200.
Submitted: May 8, 2022
Accepted: August 8, 2022
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