Journal Pre-proof

Ionic liquids synthesis and applications: An overview

Sandip K. Singh, Anthony W. Savoy

PII: S0167-7322(19)33371-9
DOI: https://doi.org/10.1016/j.molliq.2019.112038
Reference: MOLLIQ 112038

To appear in: Journal of Molecular Liquids

Received date: 14 June 2019

Revised date: 19 October 2019
Accepted date: 29 October 2019

Please cite this article as: S.K. Singh and A.W. Savoy, Ionic liquids synthesis and
applications: An overview, Journal of Molecular Liquids(2018), https://doi.org/10.1016/
j.molliq.2019.112038

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Ionic liquids synthesis and applications: An overview

Sandip K. Singh,* 1 Anthony W. Savoy,1

1 Chemical and Biological Engineering Department, Montana state University Bozeman,

MT, 59717, USA

Contents
Abstract
1. Introduction
2. Scope of ionic liquids
3. A glance at the history of ionic liquids

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4. Fundamental aspects of ionic liquids
4.1 Green aspects of ionic liquids
4.2 Environmental impacts of ionic liquids

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4.3 Purity of ionic liquids
5. Synthesis of ionic liquids
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5.1 Microwave irradiations synthesis of ionic liquids
5.2 Ultrasound-assisted reactions for ionic liquids synthesis
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6. Structural classification of ionic liquids
6.1 Task specific ionic liquids
6.2 Chiral ionic liquids
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6.3 Switchable polarity solvent ionic liquids

6.4 Bio-ionic liquids
6.5 Poly ionic liquids
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6.6 Energetic ionic liquids

6.7 Neutral ionic liquids
6.8 Protic ionic liquids
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6.9 Metallic ionic liquids

6.10 Basic ionic liquids
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6.11 Supported ionic liquids

7. Purification and recovery of ionic liquids
8. Physico-chemical properties of ionic liquids
9. Application of ionic liquids
9.1 Electro-chemistry
9.2 Solvent
9.3 Engineering
9.4 Physical chemistry
9.5 Analytical chemistry
9.6 Biological aid
Conclusions and Future Prospects
Author information
Notes
References

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Abstract
Over the past two decades, ionic liquids (ILs) have had a wide range and cutting-edge impact,
generating promising science and technologies and have also expanded exponentially in
terms of their publications. They have been utilized for both academic and industrial
applications. They are potential candidates for solving some of the major issues society is
currently faced with by emerging as a clean, efficient, and eco-friendly alternative resource of
volatile organic solvents along with many more significant benefits due to their unique
thermal, physical, chemical and biological properties. Furthermore, these properties could be
modified depending on their application by altering the combination of cations and anions.
However, their synthesis and purification require standard synthesis methods to certify their

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consistent reproducibility. The yields from ILs at large scales for the industrial applications

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along with their synthesis, toxicity and environmentally friendly nature have become the
main concerns. The aim of this review is to investigate the current literature that describes the
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cutting-edge-knowledge regarding the synthesis of various classes of homogeneous (task
specific-ILs, chiral-ILs, switchable polarity solvent ILs, bio-ILs, poly-ILs, energetic-ILs and
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many more) and heterogeneous (supported-ILs) ILs. Fundamental aspects of ILs such as the
green aspects, environmental impacts and purity of ILs are also discussed. The potential
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applications of ILs in electro-chemistry, solvent, engineering, catalysis, biological aid,

physical chemistry, analytical chemistry and many more are briefly explained. In addition,
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the explanations based on purifications and recovery of ILs by using single or combined
methods along with their physico-chemical properties were also reviewed. Moreover, the
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comprehensive study summarizes the latest progress on assorted classes of ILs along with
discussing their prospective applications in the first half. The synthesis of
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homo/heterogeneous ILs is thoroughly elaborated in the second half. Finally, the future
prospective medical applications of ILs are also mentioned.
Keywords
Bio-ionic liquids; Chiral ionic liquids; Task specific Ionic liquids; Synthesis and applications;
Structural classifications; Medicinal approaches.
Highlights
1. Synthesis of task specific, chiral, bio-ionic, energetic, etc. ILs are reviewed
2. Fundamental aspects of ILs in way of green, environmental and purity are discussed
3. Analytical, biological-aid, catalysis, etc. remarkable applications of ILs are reported
4. Purification and recovery of ILs by using single or combined methods are discussed
5. Future aspects of ILs as drugs synthesis and solubility are described
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1. Introduction
Since two decades ago, the term ionic liquids (ILs) was familiar with a very small number of
specialist research groups and even they either tried or thought that the ILs could be the best
reaction solvents for various kinds of reaction such as polymerization, alkylation, acidic
hydrolysis, Beckmann rearrangement, carbonization, esterification, depolymerization, pre-
extractions, etc. [1-10]. ILs are considered as good molecular and/or green solvents in
replacement to commonly used volatile organic solvents [11]. They are associated with
specific biological, chemical, physical and thermal properties. Normally, the term ILs are
liquids that exist in only ionic form. However, it is also distinguished in classical form as
room temperature or below ≤100 oC ILs, fused salt, molten salt, liquids organic salt, and

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many more [12]. There are few ILs that are considered exclusively ions when described as
deep eutectic solvents and few protic ILs including Olah’s reagent [13-15]. In addition, ILs

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possess a very low viscosity, low vapour pressure or non-volatility under ambient conditions,
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tuneable solubility, acidity, basicity, long range thermal stability, and very low corrosivity
relative to mineral acids and base etc. [16]. Due to their negligible vapour pressure, ILs don’t
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express the explorer risk relative to volatile organic solvents and they have also no side effect
on atmospheric photo-chemistry [12]. Moreover, the non-volatility nature of most ILs also
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lead the non-flammability under ambient conditions which could be seen with some of the
low boiling solvents such as pet ether, dichloromethane, acetone, and many more [17].
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The primary aim of this review is summarised with key literature on structural
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classification of ILs including task specific ILs, chiral ILs, switchable polarity solvent ILs,
bio-ILs, poly ILs, energetic ILs, neutral ILs, protic ILs, metallic ILs, basic ILs, and supported
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ILs, and their synthesis pathways which can be helpful in providing a brief summary for
scientists and engineers working in ILs area. Moreover, the potential applications of these ILs
were also revealed. The conclusion of this review includes a vast literature on their synthesis
and notable applications in solvent, analytical, electro-chemistry, biological aid, engineering,
physical chemistry, and many more. In this context, the synthesis of various ILs could be of
interest to electro-chemists, analysts, biologists, engineers, physical chemists and many more
chemists, particularly working in the area of ILs to set a specific-criteria to select the ideal
ILs out of million binary and 1018 ternary large number of ILs [18].

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2. Scope of Ionic Liquids

In the past decades, the frontier of ILs research emphasizes the development of green and
sustainable chemistry. Basic and applied research has developed exponentially and has
demonstrated ILs value to science with its wide range of potential applications in the fields of
chemistry, biology, physics, etc. (Figure 1, Source from ISI Web of Science). Specially, ILs
have been considered as a green solvent and/ or catalyst that can be generally used to
substitute conventional volatile organic solvents. Moreover, ILs are exhibiting several
promising perspectives in areas of synthesis, catalysis, cell biology, material science, physical
chemistry, electrochemistry, genetics heredity, nuclear physics, medicinal chemistry,
engineering and many more at both industrial and laboratory scales (Figure 2, Source from

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ISI Web of Science). Figure 2 demonstrates that the main focus of ILs is centred around

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physical chemistry, chemical engineering, material science and multidisciplinary chemistry
since they are prevalent over various applications of ILs. It might be beneficial, due to their
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continued expansion, to address ILs physico-chemical properties and many more properties
of significance.
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10000
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9000
Number of publications

8000
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7000

6000

5000
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4000

3000
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2000

1000

0
2009 2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Fig. 1. A brief history of one decade for ILs publications. (Keyword “Ionic liquids” Sourced
from ISI Web of science search).

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25000

19158
Number of publications

20000 18500

15000

10000 92799881

56736114
4495 4617
5000 32233854 3890
2509
11 29 41 58 224 356 532
0

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Web of science categories for ILs
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Fig. 2. Type of categories verses number of publications (Sourced from ISI Web of science
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search).
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3. A Glance at the History of Ionic Liquids (ILs)

The ethyl ammonium nitrate [EtNH3][NO3] (m.p. 12 oC) is the first IL introduced in the
literature in 1914 [19, 20]. In 1940, Frank Hurley and Tom Weir working at Rice Institute of
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Texas, invented salts that are liquid at room temperature. The warm powder of organic salt
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(alkyl pyridinium chloride) was added to aluminium chloride and formed a clear colourless
liquid, later known as an IL. Their discovery of the ILs remained a chemical curiosity for the
next several decades [21].
The term ionic liquids are defined as salts that exist as liquids below 100 oC or even at
room temperature. It is combination of usually organic cations (derivatives of N, N’-
substituted imidazolium, N-substituted pyridinium, tetra-alkylated ammonium, tetra-alkylated
phosphonium, etc.), and organic or inorganic anions (CF3COO, HSO4, Cl, etc.), (Figures 3, 4)
[22]. It is also called a room/low/ambient temperature molten salts/ionic fluid/liquid organic
salts/neoteric solvent. It has been stated that the physico-chemical properties of ILs is highly
viscous solvents for certain chemical reactions and differs in aqueous and conventionally
used organic media.

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ILs are considered green solvents which might be due to the following reasons.
 They are having very low vapour pressure under ambient conditions and are
therefore known as non-volatile
 ILs remain liquids over a wide range of temperature
 ILs associated with excellent lubricating and hydraulic properties
 Tuneable acidity and basicity trends of ILs
 ILs are mostly colourless and polar in nature
 ILs can take in and release gases
 ILs are mostly in hydrophilic and rarely hydrophobic nature
 They possess very low viscosity

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 They exhibited a long range of solubility of bio-polymers due to their tuneable

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combination of anions and cations
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Fig. 3. Cations used commonly in ILs synthesis

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Fig. 4. Anions used commonly in ILs synthesis

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4. Fundamental Aspects of Ionic Liquids

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Ionic liquids are essentially liquids made-up of cations and anions. These ions are usually
linked through a various kind of bonds. They are associated with a substantial amount of
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physical and chemical properties including very low to almost negligible vapor pressure,
good thermal stability, can be used as a green solvent and/ or catalyst, and many more. Due to
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their wide range of properties, they have been increasingly used in various fields of study
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such as biochemistry, engineering, physics, etc. Research pertaining to the environmental

friendliness of ILs is exciting for IL researchers. Many aspects of large-scale production and
application of ILs such as environment toxicology, hazards, cost, purity, stability are unclear.
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Remarkably, the assessment of ILs as a green solvent and/or catalyst can be derived through
the life cycle assessment of a synthesized product and/or process used to generate ILs
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compared to the same product and/ or process used for competing liquids.
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4.1. Green aspects of ionic liquids

Green chemistry or sustainable chemistry focuses on the reduction or prevention of pollution
and waste both at the laboratory and industrial scales. It also investigates the development of
economical and eco-friendly techniques that not only improve yields, but, decrease the
generation of waste [23]. A liquid or solvent can be considered as “green” if its products are
produced with minimal environmental impacts over its entire life cycle [24]. There are
several factors that are used to assess the greenness of a compound, assessing the greenness
of ILs is mainly based on the atom efficiency [25] and environmental factor (E-factor) [26].
Maximum atom economy or efficiency has resulted from the synthesis of 1-
methylimidazolium halides which occurred in one step generating a stochiometric amount of
waste [27]. Previous research has used atom efficiency as a method for determining

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greenness, but in certain scenarios, the reactions required an excessive amount of reagents so
the method is no longer considered favourable. Therefore, the E-factor term was introduced
to assess the greenness of ILs, producing zero or close to zero values for ILs reactions [27].
Energy utilization and purification are a couple of research topics that need to be considered
for improvement of the E-factor. For example, the synthesis of 1-methylimidazolium halides
via its normal synthesis and purification procedure require inefficient energy sources and
excess amounts of starting materials and organic solvents [27, 28]. To promote the greenness
in terms of energy efficiency, methods such as microwave irradiation [29, 30] and
ultrasound-assisted reactions [31, 32] are reasonable choices for ILs synthesis. Microwave
irradiation method requires low energy, promotes faster reactions rates, induces higher

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selectivity of desire product, and requires smaller quantities of reagents compared to

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traditional conductive heating procedure. In some situations, the solvent free synthesis of ILs
performed which generates less harmful waste and is easier to dispose of [27, 33].
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Other approaches might include using benign solvents, solvent free methods, solvent
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recovery, or the creation of safer chemical products, etc. for the synthesis of ILs. In a few
reports, authors have synthesized biobased derived ILs such as sugars [34], amino acids [35],
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nicotinic acid [36] and choline [37]. Deep eutectic solvents have shown promising
approaches for chemical reactions and they can be generated with the use of economy
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chemicals with minimum environmental impact [38]. Moreover, ILs have several other
benefits such as easy solvent recovery, minimum waste generation, and low emission into the
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environment [39].

4.2. Environmental impacts of ionic liquids

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The environmental impacts of ILs relative to toxicology, biodegradability and recyclability

have received a major attention from researchers when utilizing them in academic and
industrial scales. Few ILs are toxic and non-biodegradable based on their life cycle
assessments (LCA) [40]. Beside toxicology, biodegradability and recyclability factors, there
are several other assessments that influence the greenness of ILs. The effects of IL synthesis,
application, and degradation and the lifespan of its compounds in an ecosystem after
utilization have been investigated. LCA analysis has been used to characterize the potential
environmental impact through-out the life cycle of ILs by considering its use of raw materials
for synthesis and purification, applications, and recycling prior to disposal [41]. The synthesis
of ILs has not always been assumed to follow the green chemistry principle. In some cases,

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large quantities of chemicals and solvents were used to synthesize ILs and resulted in the
generation of a large amount of side products as waste, highlighting the potential negative
impacts ILs have on human beings and the environment [42].

4.3. Purity of ionic liquids

Analytical grade ILs are needed in order to generate reliable data for physical, chemical and
biological analysis [43]. Due to lack of proper and clear analysis of analytical grade ILs, the
technical grade data may be applicable. Prior to the use of technical grade ILs and their
associated risks for human and environmental, the impurities need to be quantified and
analysed [44]. (Eco)toxicological testing must be performed in order to produce the technical

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grade ILs and then compare the results with analytical grade. The data then needs to be
evaluated by using further purification to see if the high levels of toxicity were characteristic

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of in technical grade ILs. Table 1 shows a variety of impurities in ILs and their possible
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analysis using various methods [44-46].
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Table 1. Impurity types and possible analytical method for analysis
Type of impurity Analytical method
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Volatile Gas chromatography

Highly volatile Head-gas chromatography
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Halide Alkylation of amine or phosphine and titrated with Volhard

method
Lower concentration (ppm) Nessler cylinders
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Water Karl–Fischer titration

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Quantification of cations and Reversed phase or ion exchange HPLC coupled with a suitable
anions detector like UV [47]
Imidazolium cations Capillary electrophoretic method [48]
Low concentration of ionic Bioaccumulation, transformation or persistence [49]
liquids and its metabolites

5. Synthesis of Ionic Liquids (ILs)

Before describing the potential applications of ILs, their synthesis and purification needs to
be understood. The story of the first room temperature ILs started in 1914 with the synthesis
of ethylammonium nitrate (m. p. 12 oC) [50]. The ethylammonium nitrate IL was synthesized
by the addition of concentrated nitric acid with ethylamine. The additional aqueous layer was
removed by distillation to generate a pure salt, which was a liquid at room temperature.

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Generally, there are two basic methods that are employed for the synthesis of ILs [51]. The
general procedure applied for the synthesis of ILs is summarized in Scheme 1.
Normally in most of cases, a single step is required for the ILs synthesis, e.g. 1-butyl-3-
methylimidazolium chloride, ethyl-ammonium nitrate, etc. Although, many counter cations
are generated as zwitterions and further react with desired anions and form highly viscous
products. The counter cation parts of ILs are also common in commercial availability in a
halide form and require only the anion exchange reactions.

[NR3R’]+[MXY+1]-
+ Lewis acid MXy

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[R’X]
NR3 [NR3R’]+[X]-

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1. + Lewis acid [M]+[A]--MX [NR3R’]+[A]-

2. + Brønsted acid [H]+[A]--HX

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3. Ion exchange resin

Scheme 1. Typical synthesis paths for the ILs

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The anions exchange reaction occurs between halides and metal halides to form Lewis acidic
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ILs [1]. Brønsted acidic and ion exchange resin based ILs also are synthesized via anion
exchange reactions.
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The AlCl3 based salts acting as Lewis acidic ILs are broadly studied for various
applications. This is a very simple addition reaction in which Lewis acid or metal halides are
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added into the halide salts and results in the formation of respective acidic ILs with one extra
halide species [52-54]. The ratio of Lewis acid or metal halides (MXn) and quaternary salts
(Q+X-) have been shown a very simple reactions between AlCl3 and [EMIM][Cl] in Scheme
2. Similarly, few of the examples of metal halides were also used to prepare the FeCl 3, BCl3,
AlEtCl2, CuCl, and InCl3 acidic ILs with one more halide species [55-58].

Scheme 2. Series of reactions between metal halides (AlCl3) and quaternary salts
[EMIM][Cl]

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It is very simple to obtain a series of air and water stable ILs based on anion metathesis or
anion exchange reactions with 1, 3 di-alkyl, imidazolium cation. The metathesis process
occurred in presence of halide salts with sodium, potassium or silver salts of CH3COO-, NO2-,
NO3-, BF4-, SO42-, PF6- and many more free acids of corresponding anions. A few examples
of anion metathesis reactions are consolidated in Table 2.
Table 2. Anionic metathesis for the synthesis of ILs associated with 1, 3 di- alkyl
imidazolium cation
Anion Anion source(s) Chemical compound Reference
[N(CN)2] NaN(CN)2 Sodium dicyanamide [59]
[SCN] NaSCN Sodium thiocyanate [59]

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[BF4] HBF4, NH4BF4, NaBF4 Tetrafluoroboric acid, [60-65]

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Ammonium
-p tetrafluoroborate, Sodium
tetrafluoroborate
[PF6] HPF6 Hexafluorophosphoric [60, 61, 66]
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acid
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[(CF3SO2)2N] Li(CF3SO2)2N Lithium [28, 61]

bistrifluoromethylsulfonyl
imide
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[CF3SO3] CF3SO3CH3, NH4CF3SO3 Methyl [28]

trifluoromethanesulfonate,
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ammonium triflate
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[CH3CO2] AgCH3CO2 Silver acetate [62]

[CF3CO2] AgCF3CO2 Silver acetate [62]
[CF3(CF3)3CO2] KCF3(CF3)3CO2 Potassium nonafluoro-1- [28]
butanesulfonate
[NO3] AgNO3, NaNO3 Silver nitrate, sodium [28]
nitrate
[N(CN)2] AgN(CN)2 Silver dicyanamide [67]
[CB11H12] AgCB11H12 Silver dodecaborate [68]
[AuCl4] HAuCl4 Chloroauric acid [69]

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Beside these conventional methods, assorted methodologies have also been developed for
synthesizing series of ILs through microwave (MW) irradiation, sonication, macrocyclic ILs,
ring opening, acid-base neutralization, crown ethers, power ultrasound (US), and many more
[70-77]. The microwave irradiations and ultrasound-assisted ILs synthesis methods have been
associated with several advantages which will be discussed in detail in the following section.
5.1. Microwave irradiations synthesis of ionic liquids
Microwave irradiation processes have shown several advantages compared to conventional
synthesis procedures regarding its fast, selective and environmental benign behavior.
Microwave irradiation is a rapid process used to synthesize ILs. It utilizes a safe heating
source in solvent free conditions to produce high atom efficiency by improving the product

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selectivity with maximum yields in short reaction periods. Verma and Namboodiri in 2001

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established a microwave irradiation method to synthesize 1-alkyl- 3-methylimidazolium
halides (chloride and bromide) and dialkyl-3-methylimidazolium dihalides ILs without using
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any solvent, achieving > 70% yields in less than 2 min [78]. A set of imidazolium and
pyridinium cation based ILs were also synthesized by using microwave irradiations under
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solvent free conditions [79]. Similarly, chiral [80] and amino acid [81] based ILs were
synthesized by using microwave irradiations and were used for various applications. In 2006,
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Pal and Kumar synthesized a variety of imidazolium based ILs such as calamitic–calamitic
(alkoxycyanobiphe), calamitic–discotic and discotic– discotic (triphenylene) moieties by
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using microwave irradiations [82]. 1-methylimidazole, pyridine and 1-methylpyrrolidine

based cations and alkyl halides based anions as a second generation halogen free, air and
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moisture sensitive ILs were synthesized by using a combination of microwave and ultrasonic
irradiations technique [83, 84].
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5.2. Ultrasound-assisted reactions for ionic liquids synthesis

Over the last few decades, the use of ultrasound-assisted methods has gained substantial
attention from the chemical and pharma industries for the synthesis of catalysts, biofuels
production, heterocyclic intermediates, compounds of medicine and many more [85-87].
Ultrasound is an environmentally benign type of synthesis technology that has been used to
synthesize ILs under solvent free conditions and has achieved high product yields [88].
Ultrasound processes work most effectively at the interfacial layers of two immiscible liquids
via the improvement of the reaction rate and the enhancement of material transformation.
Ultrasound processes also reduce the length of reaction time. In 2002, 1-alkyl-3-
methylimidazolium based cation accompanying a set of anions such as halides (Cl, Br, I),
BF4, PF6, CF3SO3 and BPh4 were synthesized by using the ultrasound-assisted method by
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Verma’s and Lévêque’s groups [71, 74]. N‐ methyl‐ 2‐ pyrrolidinium hydrogen sulphate
based IL was synthesized with promising yields using an ultrasound-assisted method in the
absence of solvent [32].

6. Structural classification of ILs

Based on cation and anion combinations and their unique biological, physical, chemical and
thermal properties such as miscibility in aqueous and organic solvents, ionic conductivity, the
comparative acidity or basicity and others, ILs are classified into several categories [89, 90]
and the structural evaluation of IL generations [91, 92] are shown in Figure 5 as below;

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Fig. 5. Structural classification of ILs

6.1. Task specific ionic liquids (TS-ILs)
Task specific ionic liquids (TS-ILs), are known as functionalised ILs [89] [93, 94]. These ILs
have earned significant attention over the last few decades due to their specific properties
which could be tuned according to the user’s needs by altering the combination of cations and
anions. Moreover, these ILs were explored for their specific activity in assorted organic
synthesis (esterification, dehydration, pinacol reaction, etc.), catalytic reactions, and potential
trends in the chiral compounds, nanoparticle synthesis and so far [94-99]. The first TS-IL is

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3-sulphopropyl tri-phenyl phosphonium p-toluene sulphonate are shown in Figure 6 along

with a few more TS-ILs as well [4].

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Fig. 6. Structure of task specific ionic liquids

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Depending on the necessities, the synthesis of specific TS-ILs could be achieved. However,
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the synthesis of TS-ILs is a bit different and is a time-consuming process. It might be due to
the presence of assorted active functional groups which are too reactive towards the broad
range of reactants. The incorporation of N-substituted maleimide into TS-ILs was done and a
detailed synthesis procedure is given in Scheme 3 [100].

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Scheme 3. Synthesis of N-substituted maleimide task specific ILs
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Another class of TS-IL such as benzaldehyde functionalized ILs were synthesized using
quaternization of 1-methylimidazole by applying the alkyl bromide substituted benzaldehyde
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under microwave irradiation conditions (Scheme 4) [101].

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Scheme 4. Benzaldehyde functionalized task specific IL

6.2. Chiral ionic liquids (C-ILs)
Among the other class of ILs for asymmetric inductions, the C-ILs are one of the most
significant classes of TS-ILs in the area of liquid chiral chromatography, stereoselective
polymerization, synthesis of potential active chiral compounds, liquids crystal, NMR chiral

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discrimination and many more functional activities [102-104]. These ILs are promoted as
catalysts or solvents for the asymmetric synthesis of chiral compounds [105-107]. They
associate with the chiral centre either at the cation, anion, or both within the ILs. It is very
difficult to synthesize them because of their chiral nature [104, 108]. The C-ILs were
eventually used as chiral solvents for the asymmetric synthesis [109]. Figure 7 represents
some example of the C-ILs.

The synthesis of imidazolium-based C-ILs was done in multiple steps (Scheme 5) including
the condensation process between phenylethylamine, formaldehyde, glyoxal and ammonium
hydroxide in aqueous medium which provides very simple, environmental friendly methods

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[104, 110]. However, the drawback of this process is that the intermediate compounds are
gained in very low yield. It might be due to the reactions being too sensitive [104].

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Fig. 7. Structure of C-ILs

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Scheme 5. Synthesis of imidazolium-based C-IL

In good to excellent yields of chiral sulphate anions, C-ILs were synthesized as alcohols of a

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chiral pool. Moreover, the metathesis steps occurred between tetra-(n-butyl)-phosphonium
and 1-butyl-3-methylimidazolium [BMIM] counter cations (Scheme 6) [111].

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Scheme 6. Synthesis of chiral sulphate anions ILs

The [N-(3’-oxobutyl)-N-methylimidazolium][(+)-camphorsulfonate] C-IL was synthesized
using N, N’-dialkylated, prochiral imidazolium salt. For more details on synthesis of C-ILs,
see Scheme 7 [112].

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Scheme 7. Synthesis of [N-(3’-oxobutyl)-N-methyl imidazolium][(+)-camphorsulfonate] C-

IL

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Assorted C-ILs of tetraethylammonium based cation and anions as amino acids were

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prepared by using a metathesis reaction between tetraethylammonium hydroxide and a broad
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range of amino acids such as asparaginate, glutaminate, serinate, glutamate, isoleucinate,
histidinate prolinate, threoninate, methioninate (Scheme 8). However, H2O is obtained as
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by-product when the reactions are performed between tetraethylammonium hydroxide and
amino acids. Moreover, this process is more environmentally friendly due to clean side
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products that avoid the use of any metal salts or halide contaminants or ion-exchanges which
can increase the capital cost for extensive steps during purification. Significantly, this process
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occurred at room temperature because tetraethylammonium hydroxide easily protonates with

carboxylic groups that are present with amino acids and produced C-ILs. Additionally,
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tetraethylammonium based amino acid C-ILs exhibited high ionic conductivity. Therefore,
these ILs could be applied for specific applications such bio-catalysts, chiral discriminations,
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electrolytes and many more applications [113].

Scheme 8. Synthesis of tetraethylammonium based amino acid C-ILs

6.3. Switchable polarity solvent ionic liquids (SPS-ILs)
For the synthesis of SPS-ILs, an activator was applied which equilibrated it into a wide range
of lower and higher polarities for both anions and cations, respectively. Secondary amines are
typically used to get SPS-ILs by applying CO2 as an activating agents to form carbamate salt
reaction in equation 1 [114].

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A switchable IL was prepared by using N, N’ dimethyl, n-octylamine bicarbonate and carbon

dioxide mixture in which the aliquot converted the deprotonated into protonated form [115].
An alcohol was treated with either amidine or guanidine and was finally switched into CO2
which formed the low polarity to high polarity ILs at ambient pressure [116]. The switchable
high polarity ILs were obtained with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and alcohol
which switched from lower to higher polarity when treated with carbon dioxide [117].

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6.4. Bio-ionic liquids (B-ILs)

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Assorted long chains of alkyl imidazolium and alkyl benzimidazolium based ILs are
potentially toxic, poorly bio-degradable, and associated with many more issues. To overcome
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these subjects, B-ILs have been synthesized using recyclable and sustainable bio-precursors
that are minimally toxicity, environmentally friendly, bio-degradable and many more. A
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series of choline (ammonium), hydroxide cations, and different amino acid-based counter
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anions were prepared using green channel as sustainable, non-toxic bio-products without any
chemical modifications (Scheme 9) [118-122].
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Scheme 9. Synthesis of choline-based B-ILs

The toxicity and biodegradability of ILs have been inspected by the European Standards
method. The obtained standard for choline-based B-ILs showed the low toxicity and high

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biodegradability in all choline based ILs. According to the European Standards, the (2-
hydroxyethyl)-ammonium lactate was noted to have the highest bio-degradable (95%) levels.
Moreover, the synthesis of (2-hydroxyethyl)-ammonium lactates IL is given in Scheme 10
[123].

Scheme 10. Synthesis of (2-hydroxyethyl)-ammonium lactate based ILs

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6.5. Poly-ionic liquids (P-ILs)

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Poly-ionic liquids (P-ILs) or polymerized ILs are the backbone of repeating motifs of
respective monomeric units of ILs which formed as dimers, trimers, oligomers, high
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molecular weight polymers and finally into polymers or co-polymers [124-128]. Moreover,
the design selectivity of monomeric units with enriched properties and synthesis of associated
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polymeric ILs for assorted applications have seen potential in various fields such as polymer
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electrolytes, [129, 130] polyelectrolyte membranes for fuel cells [131, 132], Quasi-solid-state
electrolytes for dye sensitized solar cells [133, 134], electrolytes for batteries [135, 136],
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electrolytes for electrochemical supercapacitors [137, 138], organic transistors and memory
devices [139], modified carbon electrodes and sensors [140, 141], binders for batteries [142],
thermo-responsive PIL sol/gel transitions [143-145], pH-Triggered actuators [146, 147],
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photo-responsive materials [148, 149], solvent-responsive objects [150-152], redox-active

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[153], carbon dioxide responsive gels [154], catalysts and catalyst supports [155-157],
selective separation [158-160], carbon dioxide adsorbents [161-164] and separation [165,
166], P-IL based antimicrobial materials [167-170], photoresists and corrosion inhibitors
[171-173], dispersants and stabilizers [174, 175], and many more noteworthy applications.

Assorted P-ILs were prepared using N-(2-(dimethylamino) ethyl) methacrylate (DMAEMA)

and a series of natural carboxylic acids (RCOOH), likely acetic acid, butyric acid, benzoic
acid, oleic acid, hexanoic acid, caprylic acid, and many more. Moreover, the syntheses of
these P-ILs were obtained via free radical polymerization mechanism (Scheme 11) [176].

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Scheme 11. Free radical polymerization of monomeric P-ILs based on DMAEMA and
natural carboxylates
The pyrrolidinium-based polymeric ILs were synthesized in two separate ways. In the first
way, several anion exchanges happened with commercial poly-(diallyl dimethylammonium)
chloride IL (Scheme 12).

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Scheme 12. Synthesis of poly- (diallyl, dimethyl, ammonium) chloride P-ILs via anions
exchange
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In the second way, assorted diallyl dimethylammonium ILs with various anions were
subsequently polymerized and attained potential attentions for co-polymer synthesis due to
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their tuneable specific properties of P-ILs (Scheme 13). Moreover, both ways attained a wide
range of interest for their specific application such as solid-state Li ion batteries [177].

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Scheme 13. Synthesis of polymerised ILs with assorted diallyl dimethylammonium ILs with
various anions

6.6. Energetic ionic liquids (E-ILs)

In the last few decades, a series of E-ILs have been popularly known to have various
advantages relative to conventionally applied energetic compounds such as 2,4,6-
trinitrotoluene (TNT), 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (HNIW),
1,3,5,7-tetranitro-1,3,5,7-tetraazocane (HMX), 4,4’-Dinitro-3,3’-diazenofuroxan (DDF), and
1,3,5-(tris-nitro)perhydro-1,3,5-triazine (RDX), because of their higher density, higher
thermal stability, easy synthesis relative to conventionally used energetic materials, negligible

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vapour pressure, poor or negligible vapour toxicity, transportation that enhances safely as
well as many more applications [21, 178, 179]. A wide range of E-ILs has been prepared

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using series of cations such as 4-amino-1-methyltriazolium, 4-amino-1-ethyltriazolium, 1,5-
diamino-4-methyltetrazolium, 4-aminotriazolium, guanidinium, 4-amino-1-butyltriazolium
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and 1,5-diaminotetrazolium, with lanthanide (Ln: La, Ce) nitrate ([Ln(NO3)6]3-), based
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counter complex (Figure 8). Moreover, lanthanide-based E-ILs are associated with good to
excellent photo-chemical stability and luminescence properties as well.
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Fig. 8. Cations for E-ILs

ILs that are excellent candidates for hypergolic application were synthesized using nitro-
cyanamide anion substituted to tetrazolium and guanidinium cations and shown as below
(Scheme 14).

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Scheme 14. Hypergolic ILs based on nitro-cyanamide anion substituted to tetrazolium and

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guanidinium cations -p
The quaternization of N, N-dimethylhydrazine with alkyl halides followed by metathesis with
either silver dicyanamide or silver nitro-cyanamide to produce a series of N, N-dimethyl-
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hydrazinium hypergolic ILs (Scheme 15) [180].
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Scheme 15. Synthesis of N, N-dimethyl-hydrazinium hypergolic ILs

A wide range of N-heterocyclic based cations decorated with assorted anions such as
dicyanamide, nitro-cyanamide, and azide were applied to synthesize hypergolic ILs (Scheme
16). The reproducibility of ignition delay accumulated in the lower performance as N-NH2
and unsaturation of heterocyclic ring increased [181].

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Scheme 16. Heterogolic ILs based on heterocyclic cations and nitro-cyanamide, dicyanamide
and azide anions

6.7. Neutral ionic liquids (N-ILs)

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The counter anions of such types of ILs formed with very weak electrostatic interactions to
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counter cations which produced very low melting points and viscosity [28, 89]. However,
these N-ILs associated with good electro-chemical and thermal stability. Therefore, these N-
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ILs were typically applied as inert solvents in a wide range of open windows [28, 182-185].
Moreover, the structure of typically used counter neutral anions is shown in Figure 9 [182].
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Fig. 9. Structure of counter neutral anions

6.8. Protic ionic liquids (Pr-ILs)

The alterations between the protic and other acidic ILs are the presence of redeemable
Brønsted acidic proton(s). Hence, it can be applied as either solvents or catalysts for assorted
reactions such as hydrolysis, dehydration, fuel cell chemistry and many more [8]. The
structure of a few examples of Pr-ILs is shown below in Figure 10 [92].

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Fig. 10. Example of Pr-ILs

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The design and facile synthesis of protic or Brønsted acidic ILs (BAILs) are well known in
two steps; first step zwitterions preparation and second or final step is neutralization or ILs
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synthesis [9, 186, 187]. Moreover, the synthesis of acidic ILs is shown in Scheme 17.
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Scheme 17. Synthesis of acidic ILs

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6.9. Metallic ionic liquids (M-ILs)

Most of the metal salt ILs (M-ILs) are prepared using imidazolium or pyridium based cations
or using direct metal halides. To enhance their Brønsted and Lewis acidic properties,
bromometalate or chlorometalate salts (e.g., [Al2Br7]-, [CuCl3]-, [FeCl4]-, [AlCl3]-, [NiCl4]-,
[SnCl3]-, etc. are applied as counter anions of the ILs. Metal halides or Lewis acidic ILs are
highly viscous in nature relative to other ILs due to their special kinds of packing [188]. A
few of the metal halide based ILs are shown in Figure 11.

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Fig. 11. Examples of metal halide based ILs
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The synthesis of [(CH3)3C][Al2Br7] highly acidic ILs was done in absence of solvent using
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tert-butyl bromide and aluminium bromide (Scheme 18). Moreover, the stability of the low
nucleophilic [Al2Br7] anion was capitalized by the [(CH3)3C] cation at ambient temperature.
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Thus, it could be applied as a highly stabilized [(CH3)3C] cation [100].

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Scheme 18. Synthesis of M-IL

6.10. Basic ionic liquids (B-ILs)

Room temperature ILs are primarily classified into neutral, acidic and basic ILs. The acidic
and neutral ILs have been broadly recognized and are potentially used in many organic
transformation applications [189-199]. The class of basic ILs replaced commonly used
inorganic bases and also applied in organic transformation reactions such as Michael
addition, Markovnikov addition, aldol condensation, aza-Michael reactions and many more
[200-203]. Moreover, the basic ILs potentially offered an eco-friendly basic catalyst and have
better advantages relative to inorganic bases. Thus, the use of basic ILs have more potential

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weightage for the replacement of typical inorganic bases since they exhibited very flexible,
non-corrosive, non-volatile, solubility with many organic solvents [89, 92]. The structure of
cations and anions of basic ILs and their synthesis are shown in Figure 12 and Scheme 19,
respectively [93, 182, 204].

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Fig. 12. Structure of basic ILs
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Scheme 19. Synthesis of B-ILs

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6.11. Supported ionic liquids (S-ILs)

The use of neat ILs as solvents or catalysts are an expensive process and would be
economically unfavourable. Their highly viscous nature also creates a hurdle to achieve
maximum product yields. At large scales, disposal of the recovered impure IL is another
major issue. A lot of research has been devoted towards immobilization of ILs to overcome
the delinquent of easy separation [205-209]. Intense research has been carried out using silica
materials as surface modifiers and anchored substituents as ILs to prepare the immobilized
ILs. Moreover, the immobilizations of ILs on silica frame work have been done and 4-42
wt.% loading of ILs were done based on various physical, chemical and thermal analysis
[206-211].

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Sefat et al. have synthesized the N-(3-silicapropyl) imidazolium hydrogensulphate

immobilized ILs as solid acid catalysts [207]. The silica propyl chloride with imidazole (in
excess quantity) mixture in toluene (dried) was refluxed. The obtained dried reaction mixture
was analysed via various analytical techniques and confirmed the chemical bonds between
silica and imidazole rings. Further resultant mixture was used for N-(3-silicapropyl)
imidazolium hydrogen sulphate synthesis. Concentrated sulphuric acid was added into the
dried solid and the subsequent reaction mixture in dichloromethane was stirred under reflux
condition for 2 days. Finally, the silica supported ILs as solid catalysts were attained after
extensive washing with dichloromethane and drying the consequential mixture. From the
experimental analysis such as CHNS and thermogravimetric analysis (TGA), they claimed

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that 4 wt.% organic moieties associated with N-(3-silicapropyl) imidazolium hydrogen

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sulphate as a solid acid catalyst [207]. For more details on the synthesis procedure of
supported IL see the Scheme 20. -p
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Scheme 20. Synthesis of silica supported IL

Zhang et al. have investigated another potential approach for the preparation of silica gel
immobilized IL. Authors have done assorted physico-chemical characterizations and found
the covalent bonding between silica and IL. The CHNS and TGA analysis of obtained
immobilized IL as a solid acid catalyst exhibited that 24 wt.% anchoring of ILs on/in surface

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of silica was achieved [206]. For more details on the synthesis paths of supported acidic IL
on silica gel are specified in Scheme 21.

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Scheme 21. Synthesis of solid acid catalyst by the silica gel supported IL
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Gupta et al. have applied the sol-gel procedure for the synthesis of immobilized IL. In this
process, they applied the various levels for the preparation of ionogel samples with low
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density. Precise amounts of formic acid, tetra-ethylorthosilane, and IL were taken and
allowed the mixture to become gellified at 30 oC for 5-6 days [210]. The details for the
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preparation of immobilized IL is shown in Scheme 22.

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Scheme 22. Steps used in the synthesis of ionogels via the sol-gel path
The synthesis of 1-butyl-3-(3-triethoxysilylpropyl)-4,5-dihydroimidazolium chloride as an
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immobilised IL was carried out using N-3-(3-triethoxysilylpropyl)-4,5-dihydroimidazol and
1-chlorobutane which were covalently anchored and confirmed by several physico-chemical
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analytical techniques. Moreover, authors claimed 25 wt.% loading of IL on/in silica were
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supported [209]. For the synthesis of the immobilised IL, see Scheme 23.
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Scheme 23. Synthesis of surface anchored IL

Chrobok et al. have developed a synthesis process for the 1-methyl-3-(triethoxysilylpropyl)-
imidazolium hydrogen sulphate using silica as a support and IL as an anchored agent.
Moreover, the meso- and macro-pore silica source was applied to the synthesis of
immobilized IL as a solid acid catalyst (Scheme 24) [208].

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Scheme 24. Immobilization of IL over silica surface

In our previous paper, we have synthesized an efficient, stable, novel re-cyclable

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immobilized Brønsted acidic ionic liquid (I-BAIL) on the silica framework and obtained 42.2
wt.% immobilization of 1-methyl, 3-(3-sulphopropyl) imidazolium hydrogensulphate
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[C3SO3HMIM][HSO4] BAIL as a solid acid catalyst by applying very simple and novel
synthesis methods. The loading of BAIL was calculated based on the amount of BAIL
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consumed on the silica framework by applying assorted physical, chemical and thermal
analytical techniques. For more details on the synthesis of I-BAIL, see Scheme 25 [211].
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Scheme 25. Immobilized- Brønsted acidic IL on silica framework
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7. Purification and Recovery of Ionic Liquids
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Several methods have been discussed in this work and have been reported in literature for the
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synthesis of ILs in laboratory and industrial scales. The obtained ILs are contaminated with
generated side products such as water, salts, acids or organic solvents during the reaction.
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Purification and/ or recovery of ILs at both low scales and large scales are a major hurdle for
researchers due to their substantial physico-chemical properties. ILs associated with
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significant vapor pressures prevent the purification of ILs through common distillation
methods. Prior to or after the application of ILs to catalysis, extractions, electronic
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manufacturing, gas separation, desulphurization, genetics, and many more notable (Figure
2), the recovery and purification of ILs are essential due to economic and environmental
issues. Table 3 gives at detailed discussion of single and combined methods that can be
employed for the purification and recovery of ILs, their characteristic features, and their
advantages and disadvantages [212, 213]. Researchers should select an appropriate method to
purify and recover ILs based on their physico-chemical properties. In few works, ILs
chemists have suggested that the pre-purification of staring materials would be a good way to
partially remove the contaminations [214].

Table 3. Various methods for the purification/ recovery, characteristic features, advantages
and disadvantages of ILs

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Purification/ Characteristic feature Advantage Disadvantage

recovery
method
Distillation Distillation of volatile compounds: ILs Easy to High energy
remained as a residue perform requirement
Crystallization Solution, melt and pressure induced High purity High energy
crystallization: IL recovered as a crystal requirement
Membrane Pervaporation and pressure-driven Selective Membrane
separation membrane techniques and electrodialysis: separation, fouling
water or volatile compounds separation, ILs low energy
separation or elimination, cations or anions requirement

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cross through an ion exchange membrane

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Extraction Extraction using organic solvents, water, Easy to Special
supercritical carbon dioxide: recovery of perform,
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hydrophilic, hydrophobic or both economical requirement,
hydrophilic and hydrophobic ILs cross-
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contamination
Force field Centrifugation or gravity, and magnetic Easy to Limited
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separations: ILs separated as emulsion, operate, low application,

immiscible liquids or magnetic field energy low separation
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requirement rate
Biphasic Based on chemicals addition in water or Economical, Highly
separation vice-versa and temperature based biphasic fast, scaleup concentration
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separation: separation of biphasic by of salts or

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addition of salts, carbon dioxide or organics

polysaccharides requirement
Combined method
Membrane Pressure-driven membrane techniques and High purity Economical
separation and distillation: separation or elimination of ILs process,
distillation and removal of water or organic compounds membrane
fouling
Centrifugation Centrifugation and distillation: emulsion or High purity High energy
and distillation immiscible ILs and separation as a residue requirement

8. Physico-chemical Properties of Ionic Liquids

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A comprehensive database on the physico-chemical properties of ILs has been recorded and
measured data are reported in literature sources [215, 216]. There are a variety of physico-
chemical properties of ILs listed including density, acidity, polarity, viscosity, vapor pressure,
melting point, crystallization temperature, surface tension, conductivity, refractive index,
isentropic compressibility, expansibility, thermodynamic functions, phase equilibria, and
many more noteworthy properties. The presence of small fractions of water or any organic
solvent as an impurity has major impacts on the physico-chemical properties of ILs. It could
be expected that trace amounts of water present in ILs have a major influence on biocatalytic
activity, acidity, density, viscosity, electrical conductivity, enthalpy, surface and interfacial
tensions, molecular behaviour and so on [217, 218]. Moreover, the presence of water in ILs

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has strong intermolecular interactions such as van der Waals, hydrogen bonds, electrostatic,

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etc. and at high concentration, ILs start to dissociate into ion pairs or individual ions [217].
Rivera-Rubero et. al. have characterized the surface orientation properties of ILs and water
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using a vibrational spectroscopy [219]. Widegren et. al. have reported the effect of binary
mixtures, such as solubilized water and hydrophobic room temperature ILs, on the viscosity
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[220]. Compared to other materials, ILs show intermolecular and intramolecular interactions
that can be significantly influenced upon the structural size of cation and anion [221].
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9. Application of Ionic Liquids (ILs)

The characteristic behavior of ILs is a product of the cationic and anionic nature which
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combinedly emerged with the high class of chemical, physical, biological and thermal
stability. The minimum environmental release, noticeable task specificity with a diverse
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range of applications in electrochemistry, separation and extractions, solvent and catalysts,

analytical, physical, synthetic, biological, engineering chemistry and more [222]. Scientists
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and engineers have an expectation to develop less-toxic materials, sustainable and eco-
friendly source for chemicals, energy, fuels, etc. Therefore, ILs are considered for a wide
range of applications due to their green scenarios for solvents or catalysts [223, 224]. Some
of the potential applications are shown below [8, 223, 225-228];

9.1. Electro-chemistry
ILs are widely used in electro-chemistry due to their enlarged association with good to
excellent physico-chemical properties such as good conducting electrolytes, high viscosity,
wide windows for electro-chemical potential, high thermal stability, wide solid to liquids
range, tuneable solubility, and many more. The performance of any electro-chemical devices
are essentially based on an interface of IL/electrode properties [229]. Moreover, the

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properties of ILs/electrodes are also associated with primarily three parts; 1) conductivity of
ILs: The conductivity of any electro-chemical device is eventually based on free charge ions
and their mobility. In general, ILs have excellent ionic conductivity due to their entirely ionic
nature [230, 231]. 2) Viscosity of ILs: ILs are highly viscous due to their viscous nature, it is
called green solvents or catalysts. However, ILs exposure hazard to the atmosphere is not
clear. The high viscosity of ILs might be due to their different sized ions and cationic-anionic
interactions. The cations are generally enlarged relative to anions [232-234]. And 3) electro-
chemical potential of ILs: the electro-chemical potential properties mainly depend on
oxidation and reduction constancies of ILs. Significantly, ILs are accumulate a wide window
of electro-chemical potential in neat or with additives [221, 235, 236].

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9.2. Solvent

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Welton and co-authors have published a review in 2011 on room temperature ILs: solvent for
synthesis and catalyst applications [12]. They represented excellent physico-chemical
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properties of ILs to select as another class of solvents relative to conventionally used organic
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solvents. The ILs possessed the assorted reactions such as electron transfer reactions, acid
base reactions, microwave assistant, substitutions, elimination, addition, acid catalysed
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reactions, base or nucleophilic reactions, transition metal catalysed reactions and more [12,
237-244].
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9.3. Engineering
The development of engineering applications of ILs has been investigated approximately two
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and half decades ago, where the first report of ILs published was based on extraction.
Currently, the use of ILs is tremendously progressing in many areas of chemistry, physics,
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engineering and many more. Moreover, the first commercial plant utilizing IL has also been
established. The main advantages to use of ILs in fields of engineering is their unique
physico-chemical profiles in which they showed the complex interplayed results of molecular
hydrogen bonding, coulombic and van der Waals interactions [245-247].

9.4. Physical Chemistry

At first glance, ILs did not form any separate topics in areas of physical chemistry. Moreover,
it opens wide window due to its specific physico-chemical properties and in the beginning,
most papers in physical chemistry dealt with electrochemistry which opens an
electrochemical window and ionic conductivity [248]. Currently, its anomalous application in
assorted areas makes them very complicated solvents, materials or catalysts, and even very

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small or ppm level impurities could create lots of problems [249, 250]. They are associated
with many physical, chemical, biological and thermal properties that extend the boundaries of
conventional molecular solvents due to their large liquid ranges, wide range electrochemical
window, very high viscosity, wide ability to dissolve varieties of inorganic and organic
materials including polymer, co-polymers or macromolecules [244, 251-257], high
conductivity, wide variety of electrochemical area [258-264], etc.

9.5. Analytical Chemistry

Ionic liquids have unusual characteristic properties and holding credit for potential
environmental friendly behaviour as well. ILs showed the more and more crucial applications

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in the field of analytical processes such as chromatography, spectrometry, sensing [265, 266],
isolation, extraction, electro-analysis and used as sub class in single drop microextraction

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[267-269], environmental [270-273], bioanalytical [274, 275], extraction of hollow fibre
membrane using liquid phase microextraction [276, 277], assorted pharmaceutical entities
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[278-282], analysis of metal ions [283-287], organic environmental pollutants [288-291],
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biological matrixes [292-294], gas chromatography (GC) [43, 295, 296], GC stationary phase
[297, 298], high performance liquid chromatography (HPLC) [299-301], HPLC mobile phase
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[302-305], capillary electrophoresis [306, 307], matrix-assisted laser desorption ionization

time of flight (MALDI-TOF) [308-314]. Due to their unique properties, ILs have been
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successfully used in wide range of analytical chemistry [315].

9.6. Biological Aid

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Apart from using conventional organic solvents in drug discovery technology, the use of ILs
as an alternate reaction media are governing more attention and became more popular in
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recent years [243]. ILs are ionic chemical compounds and gained assorted submissions in
many fields of modern science and technologies. It might all be plausible due to their
tuneable exceptional properties which can be altered by changing the cations and anions ratio
specific to their need. Apart from chemical and physical properties of ILs, they associate with
high biological activity which is attracting significantly more interest from ecologists,
medicinal scientist and biochemists. Moreover, they have been elaborated for biological
activity as antimicrobial, cytotoxic, etc. and in the arena of drug delivery and drug synthesis
applications as well [316-318].
Conclusions and Prospects
Ionic liquids offer an interesting alternative to the various conventionally used volatile
organic solvents, mineral acids, bases, solid acids and many more. It might be due to their

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non-corrosive as green and eco-friendly natures, they can be used as solvents or catalysts for
wide range of organic transformation or synthesis procedures. In addition, ILs can be
synthesized in single step (e.g. neutral ILs) or multiple steps (e.g. task specific, poly,
supported, chiral, bio ILs etc.). They associate with flexible to modulate thermal, chemical,
biological and physical potential properties which could be achieved by altering the
combinations of cations and anions ratios, which has attracted interests for industrial and
academic applications in the last few decades. Moreover, the scope and potential applications
of these ILs have been explored and need to be continued in sustainable ways in various
fields such as analytical, solvents, catalysts, polymers, electrodes, energy storage, medical
aids, and many more. The use of single or combined methods for purification and recovery of

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ILs have been discussed. The methods have improved the levels of ILs purity and recovery

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substantially in both laboratory and industrial scales. One of the most exciting and
challenging areas is the potential welfares have been moderately pungent for the vital
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applications of ILs to the perceptions of bio-refinery to bio-chemicals which are the future
need of green and clean energy resources [319].
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The growing concerns to the development of pharmaceuticals and many more prospective
applications as discussed above using green and clean ILs requires a profound consideration
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in both their reproducible synthesis at large scales and their purity at microscopic levels. It is
assumed that many of the pharmaceutical industries are constructed on solid or solid
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processing and they are using the volatile organic solvents, which are also meant to dissolve
the drugs. However, they are unable to recycle and also able to partially solubilize them,
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whereas, ILs could be an emerging, clean and green solvents due to their broad range of
polarities and combinations of cations (particularly organic) and anions (mixture of organic
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and inorganic) which could be served to easy solubilize extensive range of drugs.

Author information
Corresponding author
*E-mail: [email protected]
Phone: +1-406-539-9338
Notes
The authors declare no competing financial interest.
Acknowledgement
SKS and AWS would like to thank the reviewers for their insightful discussions and
suggestions to substantially improve the quality of this review.

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[2] J.-F. Huang, G.A. Baker, H. Luo, K. Hong, Q.-F. Li, N.J. Bjerrum, S. Dai, Bronsted acidic room
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Green Chem., 8 (2006) 599-602.
[3] D. Fang, J. Yang, C. Jiao, Dicationic Ionic Liquids as Environmentally Benign Catalysts for
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[4] A.C. Cole, J.L. Jensen, I. Ntai, K.L.T. Tran, K.J. Weaver, D.C. Forbes, J.H. Davis, Novel
Brønsted Acidic Ionic Liquids and Their Use as Dual Solvent−Catalysts, J. Am. Chem. Soc., 124

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[5] R. Kore, R. Srivastava, Synthesis and applications of highly efficient, reusable, sulfonic acid

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group functionalized Brönsted acidic ionic liquid catalysts, Catal. Commun., 12 (2011) 1420-1424.
[6] B.M. Matsagar, P.L. Dhepe, Bronsted acidic ionic liquid-catalyzed conversion of hemicellulose
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Declaration of Competing Interest

There are no conflicts to declare.

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Graphical abstract
Strcutural classifications, synthesis and potential applications based on the cutting-edge-
knowledge of ionic liquds have explored.

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