Review

pubs.acs.org/CR

Acidic Ionic Liquids

Ananda S. Amarasekara*
Department of Chemistry, Prairie View A&M University, Prairie View, Texas 77446, United States

ABSTRACT: Ionic liquid with acidic properties is an important branch in the wide ionic
liquid field and the aim of this article is to cover all aspects of these acidic ionic liquids,
especially focusing on the developments in the last four years. The structural diversity and
synthesis of acidic ionic liquids are discussed in the introduction sections of this review. In
addition, an unambiguous classification system for various types of acidic ionic liquids is
presented in the introduction. The physical properties including acidity, thermo-physical
properties, ionic conductivity, spectroscopy, and computational studies on acidic ionic liquids
are covered in the next sections. The final section provides a comprehensive review on
applications of acidic ionic liquids in a wide array of fields including catalysis, CO2 fixation,
ionogel, electrolyte, fuel-cell, membrane, biomass processing, biodiesel synthesis, desulfuriza-
tion of gasoline/diesel, metal processing, and metal electrodeposition.

CONTENTS 7.4. Ionic Conductivity 6147

7.5. Spectroscopy 6147
1. Introduction 6134 7.6. Miscellaneous Physical Properties 6147
2. Lewis Acidic Ionic Liquids 6135 8. Computational Studies on Acidic Ionic Liquids 6147
2.1. Lewis Acidic Ionic Liquids with Electron 8.1. Computational Studies on Acidity and Other
Accepting Ability in the Anion 6135 Physical Properties 6147
2.1.1. Haloaluminate Lewis Acidic Ionic 8.2. Computational Studies on Acidic Ionic liquid
Liquids 6135 Catalysis 6147
2.1.2. Lewis Acidic Ionic Liquids with Zn, Sn, 9. Applications of Acidic Ionic Liquids 6148
and Other Metallic Anions 6135 9.1. Catalysis Applications 6148
2.2. Lewis Acidic Ionic Liquids with Electron 9.1.1. Esterification and Saponification 6148
Accepting Ability in the Cation 6137 9.1.2. Alkylation 6148
3. Brö nsted Acidic Ionic Liquids 6137 9.1.3. Acetalization 6151
3.1. Protic Acidic Ionic Liquids with Acidic 9.1.4. Heterocyclic Synthesis 6152
Hydrogens on Cation 6137 9.1.5. Carbonium Ion Generation and Rear-
3.2. Protic Acidic Ionic Liquids with Acidic rangements 6152
Hydrogens on Anion 6138 9.1.6. Dehydration 6152
3.3. Protic Acidic Ionic Liquids with Acidic 9.1.7. Oxidation 6152
Hydrogens on Cation and Anion 6139 9.1.8. Polymerization and Related Reactions 6154
3.4. Brö nsted Acidic Ionic Liquids with Acidic 9.1.9. Miscellaneous Catalysis Applications 6154
Hydrogens on a Functional Group 6139 9.2. Carbon Dioxide Dissolution and Fixation 6155
3.5. Brö nsted Acidic Ionic Liquids with Acidic 9.2.1. Cyclic Carbonate Synthesis 6155
Hydrogens on Functional Groups and on an 9.2.2. Urea Synthesis 6155
Anion or Cation 6139 9.3. Ionogels, Electrolyte, Battery, and Capacitor
4. Brö nsted-Lewis Acidic Ionic Liquids 6140 Applications 6155
5. Polymeric Acidic Ionic Liquids 6141 9.4. Fuel-Cell Applications 6156
5.1. Acidic Ionic Liquid Groups Grafted onto an 9.5. Electrophoresis Applications 6156
Existing Polymer 6141 9.6. Membrane Applications 6156
5.2. Polymerization of an Acidic Ionic Liquid 9.7. Conversion of Biomass to Renewable Feed-
Monomer 6141 stock Chemicals 6157
6. Immobilized Acidic Ionic Liquids 6141 9.7.1. Renewable Furans, Levulinic Acid, and
6.1. Immobilized on Inorganic Supports 6141 Related Compounds 6157
6.2. Immobilized on Organic Supports 6142 9.7.2. Depolymerization of Cellulose 6158
7. Physical Properties of Acidic Ionic Liquids 6142 9.7.3. Depolymerization of Lignin 6161
7.1. Solubility, Density, Viscosity, and Related
Properties 6142
7.2. Acidity 6144 Received: December 28, 2015
7.3. Thermo-Physical Properties 6146 Published: May 13, 2016

© 2016 American Chemical Society 6133 DOI: 10.1021/acs.chemrev.5b00763

Chem. Rev. 2016, 116, 6133−6183
Chemical Reviews
9.7.4. Pretreatment of Biomass 6161
9.8. Biodiesel Synthesis 6161
9.9. Desulfurization of Gasoline, Diesel, and
Petroleum Refinery Applications 6161
9.10. Metal Extractions and Processing 6162
9.11. Electrodeposition of Metals 6162
9.12. Miscellaneous Applications of Acidic Ionic
Liquids 6162
10. Concluding Remarks 6162
Author Information 6163
Corresponding Author 6163
Notes 6163
Biography 6163
Acknowledgments 6163
Abbreviations 6163
References 6163
1. INTRODUCTION
Since the 1999 review titled “Room-Temperature Ionic
Liquids: Solvents for Synthesis and Catalysis” by Welton,1
there are about a dozen books2−13 published with ionic liquids
(ILs) in the title, and ionic liquids have grown in to a major
research area in the last 15 years. A March 30th, 2016 search
using CAS SciFinder and Scopus for review articles with the
keyword “Ionic liquids” in the title yielded 727 and 694 review
papers, respectively. As a number of previous reviews have
established the definition of ionic liquid as a salt in the liquid
state, this review will also follow the same description. In some
contexts, the term has been restricted to salts whose melting
point is below some arbitrary temperature, typically 100 °C.
Thus, it is important to keep in mind the terms such as room-
temperature ionic liquid, molten salt, liquid organic salt, fused
salt, liquid electrolytes, ionic melts, ionic fluids, fused salts, and
liquid salts have all been used to describe these salts in the
liquid phase. Since we have come a long way from the initial
understanding of ionic liquids as nonvolatile solvents for
reactions; today the subject area of ionic liquids is diverse and
wide, and it is impossible to analyze in a single review or a
book. Hence, most recent reviews, book chapters, and books
are evaluating a branch, subgroup, or application in the general
subject area of ionic liquids.
Numerous review articles on neutral ionic liquids can be
referred to for information that is outside the scope of this
article. These reviews have focused on a particular application
of neutral nonfunctionalized or functionalized ionic liquids; for
example, chemical catalysis−solvents,14−26 biocatalysis,27−34
chromatography and analysis,35−44 biomass pretreatment and
processing45−50 electrochemical applications51−54,12,55−58 or
engineering fluids,59−62 and other miscellaneous applica-
tions63−65,23,66−70 are covered in those articles. This review is
designed to give a comprehensive coverage of a selected class of
ionic liquids called acidic ionic liquids (AILs). An acidic ionic
liquid can be defined as a low melting ionic salt with acidic
characteristics. The acidic character can be Brönsted, Lewis, or
a combination of Brönsted and Lewis acid type. Then the acidic
function(s) or group(s) can be either in the cation, anion, or
both. The AILs are a part of a wider group of functionalized
ionic liquids. As described above, it is important to note that
the majority of the ionic liquids known and described in the
literature are neutral ionic liquids, and this review will
concentrate only the synthesis, properties, and applications
the acidic subgroup.
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Review
Then, since 2006 there are five review articles published with
the word “acidic ionic liquids” in the title.71−75 Of the more
recent three reviews in this sub group; the article titled “Acidic
Brönsted ionic liquids” with 123 references was published in
2010.73 The second with title “Structural effects on the
physicochemical and catalytic properties of acidic ionic liquids:
An overview” by Chiappe and Rajamani with 182 references
appeared in 2011.74 The most recent review titled “The use of
supported acidic ionic liquids in organic synthesis” with 79
references by Skoda-Foldes describes recent applications of
acidic ionic liquids supported on organic and inorganic
supports for catalysis applications.75 In addition a 2014 review
titled “Halometallate ionic liquids-revisited” and a 2015 review
titled “Acidic ionic liquids as sustainable approach of cellulose
and lignocellulosic biomass conversion without additional
catalysts” focused on specialized applications of acidic ionic
liquids as well.76,77 The scope of this review is wider than the
five previous reviews on this subdiscipline. This comprehensive
review on acidic ionic liquids is an attempt to cover all types of
acidic ionic liquids, their synthesis properties, and applications.
It is important to define the nomenclature system used in
this acidic ionic liquid review at the introduction. As the
number of ionic liquids and the number of research groups
working on ionic liquids have proliferated, especially in the
neutral ionic liquid arena, there a number of deferent
abbreviations for ionic liquids in the literature. However, the
system defined by Hallett and Welton for neutral ionic liquids
in their 2011 review article in “Chemical Reviews” is the widely
used system today.14 Despite this many articles in this area still
use their own abbreviations and naming systems, creating some
confusion. Thus, it is about time to adopt a uniform
nomenclature for ionic liquids as in other well developed
branches such as organometallic complexes. For instance most
abbreviations used in the literature derive from the name of the
ion; for example: [bmim]+ and [BMIM]+ both refer to the 1-
butyl-3-methylimidazolium cation. Nevertheless, there are
ambiguities in this naming system, such as [pmim]+, which
can be used for the 1-propyl-3-methylimidazolium cation as
well as for the 1-pentyl-3-methyllimidazolium cation. To avoid
this complication, we have chosen to use an alphanumeric
system to describe the alkyl chains, with an alphabetic
abbreviation for the charged center. In this system the 1-
butyl-3-methylimidazolium cation becomes [C4C1im]+. If the
alkyl chain is not linear, like for instance, the 1-tert-butyl-3-
methylimidazolium cation, it can be abbreviated as [tC4C1im]+.
In the case of functionalized ionic liquids with a functional
group in the side chain the type and position of the functional
group can be noted as well. In the case of an alcohol group on
the terminal carbon of the butyl chain, the abbreviation is
[(HO)4C4C1im]+, where the position of the OH group is
shown as 4 as a superscript between the group and the attached
carbon. Following this system described in the 2011 Hallett and
Welton’s review, this review extrapolates the same set of rules
to functionalized class “acidic ionic liquids”. For example the
most widely described acidic ionic liquid 1-(3-propylsulfonic)-
3 - m e t h y l im id az o li u m ch lo r id e i s a b br e vi a t e d a s
[(HSO3)3C3C1im][Cl]. 1-(4-butylsulfonic)-3-methylimidazo-
lium hydrogensulfate is [(HSO3)4C4C1im][HSO4]. Some
common acidic ionic liquids and their nomenclature used in
this review are shown in Figure 1.
The AILs with one acid function can be classified according
to the type of acid function in the molecule. The Lewis acidic
ionic liquids (LAILs) display their acidity due to a deficiency in
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Chemical Reviews
Figure 1. Common acidic ionic liquids.
electrons, whereas Brönsted acidic ionic liquids (BAILs) display
their acidity due to ionizable protons. Then there are AILs with
more than one Brö nsted or Lewis acid function and
combinations of Brönsted and Lewis acid functions as well.
2. LEWIS ACIDIC IONIC LIQUIDS
In the Lewis theory of acid−base reactions, the base donates a
pair of electrons and the acid accepts a pair of electrons. For
6135
Review
Lewis acidic ionic liquids (LAILs) this electron accepting ability
may be located in the anion or cation. However, most of the
known LAILs are in the electron accepting ability in the anion
group. Some of these ILs are described as a part of a larger set
in a 2014 review titled “Halometallate ionic liquids-revisited” as
well.76
2.1. Lewis Acidic Ionic Liquids with Electron Accepting
Ability in the Anion
A selected set of LAILs with electron accepting ability in the
anion is shown in Figure 2; they are generally prepared by
reacting a neutral ionic liquid with a Lewis acidic metal halide
under anhydrous conditions.
Figure 2. Lewis acidic ionic liquids with electron accepting ability in
the anion.
2.1.1. Haloaluminate Lewis Acidic Ionic Liquids. Lewis
acidic ionic liquids with aluminum halide anions are a major
subgroup in LAILs known for over 60 years.78,79 An early
example of haloaluminates can be found in Hurley and Wier’s
patents, where they used a mixture of 37 mol percent
ethylpyridinium chloride and 63 mol percent aluminum
chloride for the electrodeposition of aluminum.80,81 However,
the systematic study of haloaluminate Lewis acidic ionic liquids
started later when Osteryoung and co-workers rediscovered
these salts and published their synthesis and electrochemical
applications.82,83 In a follow up work Wilkes et al. reported the
synthesis of dialkylimidazolium chloroaluminate Lewis acidic
ionic liquids, their electrochemistry and spectroscopy.84 All
chloroaluminate ionic liquids are moisture sensitive materials
that require handling in dryboxes; however these materials
generally exhibit good electrical conductivities and low
viscosities. The widely studied chloroaluminate ionic liquids
are with common cations of pyridinium, alkyl imidazolium and
tetra-alkyl ammonium types. Depending on the molar ratio of
aluminum chloride to neutral ionic liquid organic chloride salt
[Cat]Cl, several negatively charged species are often present in
equilibrium. The formation of these chloroaluminate anions
AlCl4¯, Al2Cl7¯, and Al3Cl10¯ are shown in the equations below:
[Cat]Cl + AlCl3 ⇄ [Cat]AlCl4
[Cat]AlCl4 + AlCl3 ⇄ [Cat]Al 2Cl 7
[Cat]Al 2Cl 7 + AlCl3 ⇄ [Cat]Al3Cl10
A number of research groups have studied the synthesis and
physical properties such as acidity,85,86 conductivity,87,88
electrodeposition,89 electrochemical reduction,90 density, and
viscosity91−93 of these chloroaluminate ionic liquids.
2.1.2. Lewis Acidic Ionic Liquids with Zn, Sn, and
Other Metallic Anions. One main disadvantage of chlor-
oaluminate ionic liquids is their moisture sensitivity. The zinc
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based ionic liquids have been developed as a possible solution
to this problem as well as a part of a search for lower melting
LAILs.94−97 The initial examples of these LAILs were produced
using zinc chloride with pyridinium, ethylphenylammonium,98
and imidazolium salts.99−102 However, these LAILS showed
higher melting points than the corresponding chloroaluminate
melts but are still fluids at ambient temperatures. During the
same period it was also shown that FeCl2, FeCl3,103 and
stannous salts104 form ionic liquids with 1-butyl-3-methylimi-
dazolium chloride.
The continuous search for moisture stable LAILs with wider
electrochemical applications led to the development of Zn and
Sn based quaternary ammonium type ionic liquids and
especially salts such as choline chloride LAILs.94,105−108 The
melting behavior of mixtures of various ammonium salts with
zinc and tin chlorides is an interesting example; some of the
results from Davies and co-workers study are shown in Table
1.94 As revealed in this study; with salts of symmetrical cations,
Table 1. Freezing Points for the LAIL Materials Formed
from Heating a Quaternary Ammonium Chloride and MCl2
(M = Zn, Sn) in a 1:2 mol Ratio94
cation M2+ freezing point/°C
+
H4N Zn >200
Me4N+ Zn >200
Et4N+ Zn 90−92
Me3N+Et Zn 53−55
Me3N+CH2CH2OH Zn 23−25
Me3N+CH2CH2Cl Zn 23−25
Me3N+CH2CH2OC(O)Me Zn 30−32
Me3N+CH2CH2OC(O)Ph Zn 46−48
Me3N+CH2CH2OH Sn 43−45
Me3N+CH2CH2Cl Sn 69−71
Me3N+CH2CH2OC(O)Me Sn 13−15
Me3N+CH2CH2OH Zn/Sna 21−23
a
The ratio [Me3NCH2CH2OH]Cl:ZnCl2:SnCl2 was 1:1:1.
H4NCl and Me4NCl, no liquid was formed below 200 °C,
whereas with the longer ethyl chain in Et4NCl the freezing
point was 90 °C. The unsymmetrical ammonium salt Me3NEt+
gave a freezing range of 53−55 °C, which is a reduction of 35
or 140 °C compared with Et4N+ and Me4N+ cations,
respectively. In addition, they found that functionalized ethyl
chains such as Me3N+C2H4Y give even lower freezing points;
for example, if Y = OH or Cl, truly room temperature ionic
liquids are observed with freezing points in the 23−25 °C
range. Even when the substituent is significantly larger, for
instance, Y = OC(O)Me or OC(O)Ph, the salts formed have
lower freezing points than for Me3N+Et salt. These results
suggest that both lower symmetry and the presence of a
functional group may reduce the freezing points of the salts
formed, though the exact role of the functional substituent is
not yet clear. In all cases the liquids formed are viscous and
hygroscopic but moisture-stable, so these materials can be easily
prepared and stored without the need for special equipment.105
The Zn and Sn containing choline based LAILs are a
particularly attractive group in ammonium salts as they are
water and air insensitive. In addition, they are easy to prepare
and relatively inexpensive, enabling their use in large-scale
applications. The choline based zinc halide ionic liquids have
been used in numerous applications including zinc alloy
6136
deposition,109 battery electrolytes, and as catalysts in Diels−
Alder and Fisher indole synthesis.95,110
The identification of various metal halide species in the metal
based LAILs is an important aspect in their studies and
applications. The most widely used techniques are FAB-mass
spectra and NMR spectroscopy. For example, three main
chlorozincate anions in choline chloride (ChCl)/zinc chloride
1:2 composition ionic liquid have been identified as ZnCl3−
(m/z 171), Zn2Cl5− (m/z 307), and Zn3Cl7− (m/z 443) by
FAB-mass spectra. In addition higher clusters are also
detectable at very low intensities. The formation of these
species can be explained in a series of equilibriums as shown in
the following equations:
2ZnCl 2 + Ch+Cl− ⇄ Zn2Cl5− + Ch+
2Zn2Cl5− ⇄ ZnCl3− + Zn3Cl 7−
Zn2Cl5− ⇄ ZnCl 2 + ZnCl3−
In the case of Sn-based ionic liquids, FAB mass spectroscopy
showed the presence of SnCl3− (m/z 225) and Sn2Cl5− (m/z
412). For the iron system the only anionic species detected was
FeCl4− (m/z 197). Interestingly Sn3Cl7− or Fe2Cl7− clusters
could not be detected in Sn and Fe systems; most likely these
species are too unstable to be observed using FAB-MS.105
NMR spectroscopy is another technique used in investigating
different species present in LAILs.111−115 Santini et al.
examined the mixtures of ZnCl2 and 1-butyl-2,3-dimethyl
imidazolium chloride [C4(C1)2im][Cl] using NMR and mass
spectrometry.116 In this study they found that [C4(C1)2im][Cl]
and [C4(C1)2im][ZnCl3] are present at χZnCl2 < 0.5 as well as
pure [C 4(C 1 ) 2 im][ZnCl 3] at χZnCl2 = 0.5. Whereas a
combination of [C4(C1)2im][ZnCl3] and [C4(C1)2im][Zn3Cl7]
was found at χZnCl2 > 0.5.116
Terrade and co-workers have investigated the anionic
speciation of chlorostannate(II) LAILs, by 119Sn NMR
spectroscopy, X-ray photoelectron spectroscopy, and viscom-
etry.114 In addition, they have examined the crystalline samples
using single-crystal X-ray crystallography, Raman spectroscopy,
and differential scanning calorimetry. Both liquid and solid
systems (crystallized from the melt) contained [SnCl3]− in
equilibrium with Cl− in samples at χSnCl2 < 0.50; [SnCl3]− in
equilibrium with [Sn2Cl5]− at χSnCl2 > 0.50, and only [SnCl3]−
at χSnCl2 = 0.50. In addition, Sn(II)chloride was found to
precipitate when χSnCl2 > 0.63. Furthermore, the Lewis acidity
of the Sn(II)chloride based systems expressed by their
Gutmann acceptor number has been determined as a function
of the composition χSnCl2, to reveal that Lewis acidity for χSnCl2
> 0.50 samples are comparable to the analogous systems based
on zinc(II). Furthermore, it was possible to estimate the change
in the Lewis basicity of the anion using 1H NMR spectroscopy,
by comparison of the chemical shifts of the C-2 hydrogen in the
imidazolium ring. Finally, compositions containing free chloride
anions (χSnCl2 < 0.50) were found to oxidize slowly in air to
form a chlorostannate(IV) ionic liquid containing the [SnCl6]2−
anion.114
In another example Lungwitz and Spange studied the
hydrogen-bond-accepting (HBA) and donating (HBD) param-
eters of LAILs with halogeno complex anions by 1H NMR
spectroscopy.112 The imidazolium cation served both as part of
the LAIL and as a 1H NMR probe. The HBA and HBD
strengths were calculated in terms of the empirical polarity
parameters β and α according to the Kamlet−Taft equation.
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The study included 1-butyl-3-methylimidazolium ionic liquid
with chloroaluminates of various mole fractions from 0 to 0.67
of AlCl3. The 1H NMR chemical shift of the C-2 proton in the
imidazolium cation was found to be dependent on the HBA
ability of the corresponding anion. For the chloroaluminates
the HBA ability decreased and the HBD ability increased with
increasing mole fraction of the Lewis acid. In general, the HBA
strength of the LAILs studied increased in the following order:
MoCl6− < Al2Cl7− < AlCl4− < WCl7− < I5− < SnCl5− < I3− <
SbCl6− < TiCl5− < BBr4− < SnCl3−. The corresponding HBD
ability showed a reverse trend.112
The Gutmann acceptor number (AN) is a quantitative
measure of Lewis acidity and has been estimated for LAILs by
31
P NMR chemical shifts using triethylphosphine oxide as a
probe molecule. In this study chlorometallate ionic liquids
based on Group 3 metals (Al(III), Ga(III), and In(III)) with 1-
octyl-3-methylimidazolium cation were used and the results
were compared with a range ANs of standard molecular
solvents and acids.111
A few studies reported the X-ray structures of LAILs,114
where Zhou and Sasaki reported structures of several metal
co ntainin g I Ls in clud ing [C 4 C 1 im] 2 [ S nCl 4 ] an d
[C4C1im]2[ZnCl4].117 During this work they reported an
interesting correlation between the symmetry of the metal-
containing anions and the melting points of the investigated
ILs, for a series of LAILs with the same cation and molar ratio
of anion to cation (1:2),117 where they found that melting
points decreased in the order Oh > D4h > Td > D2d > C2v.117
Several iron based LAILs with common cations are known
and these ionic liquids are especially useful in catalysis
applications. These materials are a particularly attractive
group due to moisture stability, magnetic liquid proper-
ties,118−125 and the ability to form ionogels.126,127 Some of
the noticeable catalysis applications include [C4C1im]Cl-
1.5FeCl3 in glycosidation of 3,4,6-tri-O-acetyl-d-glucal with
alcohols to give glycopyranosides,128 [C4C1im][FeCl4] in
Michael addition,129 polystyrene-supported Lewis acidic iron-
containing ionic liquid for converting CO2 into cyclic
carbonate,130 [C4C1im][FeCl4] for benzylation of various
arenes/heteroarenes into the diarylmethanes,131 and glycol-
ysis.132 In addition [C4C1im][FeCl4] system has been used as a
desulfurizing agent133,134 and 1-ethyl-3-methylimidazolium
chloride ([C2C1im]Cl) with iron chlorides FeCl2 and FeCl3,
for rechargeable batteries135 as well. Xia and Taubert have
reported another interesting property of FeCl4− anion
containing LAILs.136 In this instance, 1-butyl-3-methylimida-
zolium tetrachloroferrate(III) [C4C1im][FeCl4] and 1-dodecyl-
3-methylimidazolium tetrachloroferrate(III) [C12C1im][FeCl4]
[FeCl4] exhibited a thermally induced demixing with water
(thermomorphism). Furthermore, they noticed that phase
separation temperature varies with LAILs weight fraction in
water and could be tuned between 100 °C and room
temperature.136
Yoshida and Saito reported the influence of structural
variations such as changing the alkyl chain (R) length in the
cation and substituting the halides (X) in the anion on their
thermal behavior, IR, VU−vis spectra, density, viscosity, ionic
conductivity, and magnetic properties for a series of para-
magnetic ionic liquids.137 These LAILs were comprised of 1-
alkyl-3-methylimidazolium cation (R = Et, nBu, nhexyl and
n
octyl) and tetrahalogenoferrate(III) FeX4− anion (X = Cl and
Br). They found that the elongation of the alkyl chain leads to a
pronounced reduction of fluidity and ionic conductivity, and
6137
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the replacement of chlorides with bromides leads to a similar
tendency toward ionic diffusion. It would seem that ion
association is less pronounced in the FeBr4− salts, which could
be rationalized on the basis of a more significant nephelauxetic
effect together with the lower molar concentration in the FeBr4
salts.137
2.2. Lewis Acidic Ionic Liquids with Electron Accepting
Ability in the Cation
Lewis acidic ionic liquids with electron accepting ability in the
cation is not common in LAILs and a preparation of a boron
containing example is shown in Figure 3.138
Figure 3. Synthesis of LAILs with electron accepting ability in the
cation.
3. BRÖ NSTED ACIDIC IONIC LIQUIDS
The Brönsted acidic property of a substance is based on the
Brönsted−Lowry theory proposed independently by Johannes
Nicolaus Brönsted and Thomas Martin Lowry in 1923.
According to this theory Brönsted acid is a substance that
donates a hydrogen ion (H+) or proton. Brönsted base is a
substance that accepts a hydrogen ion (H+) or proton.
Therefore, Brönsted acidic ionic liquid (BAIL) can be defined
as an ionic liquid substance that can donate a hydrogen ion
(H+) or proton. Those donating or easily releasable proton(s)
in the BAIL can reside in a number of locations in the structure
and can be further classified based on the location of the acidic
proton(s). The most common locations you can find the acidic
proton(s) are nitrogen or oxygen atoms, in the anion, and in
acidic functional groups (e.g., SO3H, CO2H) attached to the
cation. In addition to this BAILs can be classified based on the
synthesis method as well. The acidic ionic liquids are prepared
by reacting a Brönsted base and a Brönsted acid. The BAILs
with one or more acidic hydrogen(s) residing on N or O atoms
are known as protic ionic liquids (PILs) as well. In this review
protic ionic liquids with H+ in cations and anions will be
referred to as a part of the larger collection of Brönsted acidic
ionic liquids. Then the third group is acid group functionalized
ILs and in these compounds the acid group is generally
tethered to the cation. Therefore, BAILs can be further
classified into five different sub groups as shown below.
3.1. Protic Acidic Ionic Liquids with Acidic Hydrogens on
Cation
The Brönsted acidic ionic liquids with acidic hydrogens residing
on the cationic side can be considered as a major group; this
sub group is commonly refered to as “protic ionic liquids” as
well. However, in this review the classification is further refined
as protic acidic ionic liquids with acidic hydrogens on cation
and anion as two separate groups due to rapid growth in the
field. Greaves and Grummond have reviewed the literature on
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properties and applications of protic ionic liquids until 2008.139
This type of ionic liquid is formed by stoichiometric reactions
between Brönsted acids and Brönsted bases. There are many
combinations of Brönsted acids and bases that can give stable
salts, but to obtain a true IL, it is necessary to have complete
(conventionally ∼99.9%) transfer of the proton from the acid
to the base. Generally, the aqueous pKa values of the precursor
acids and bases are regarded as predictive of the behavior of the
formed protic ILs; more accurately, ΔpKa values greater than
8−10 [ΔpKa = pKa(base) − pKa(acid)] are reported to
produce protic ILs of ideal ionicity.140 As far as we are aware,
the first ionic liquid was discovered by Gabriel in 1888, and this
compound, ethanolammonium nitrate, is also a protic acidic
ionic liquid with acidic hydrogens on the cation.141,142 As
mentioned earlier this type of BAIL is synthesized by reacting
equimolar amounts of Brönsted acids and Brönsted bases as
shown in Figure 4.
Figure 4. Synthesis of protic acidic ionic liquids with acidic hydrogens
on cation by proton transfer from Brönsted acid to Brönsted base.
Some selected examples of protic acidic ionic liquids with
acidic hydrogens on cation are triethylammonium bromide,143
bis(tetrafluoromethylsulfonyl)amide,144 pyridinium bromide,143
1-methylimidazolium chloride, bromide, iodide,143 BF4−,
CF3SO3−,145 1-butylimidazolium chloride,143 2-n‑butyl-1,1,3,3-
tetramethylguanidinium acetate,146 pyrolidonium, and lactam
based BAILs.147 Some of these Brönsted acidic ionic liquids are
shown in Figure 5. The tetramethylguanidinium compound is a
particularly interesting Brönsted acidic ionic liquid because it
act as a duel acid−base; H on N-2 acts as the Brönsted acid site,
whereas the N1 and N3 are tertiary amine groups with basic
properties.
In an ideal protic acidic ionic liquid synthesis, the Brönsted
acid and base react completely to produce the PAIL. However,
in practice the proton transfer may be less than complete,
resulting in the neutral acid and base species being present. In
addition, aggregation or association of either ions or neutral
species can also occur. Therefore, there are attempts to measure
the ionic character or ionicity of the PAILs to evaluate the
proton transfer in the final product.148−153
One of the widely used methods to measure ionicity for the
characterization of ionic liquids is the log(equivalent con-
ductivity) versus log(fluidity) plot known as the Walden
Figure 5. Selected examples of protic ionic liquids with H+ on cation.
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plot.154−162 The Walden plot that makes allowance for
differences in ion sizes is shown to be an improvement to
this early approach, and in some cases it is feasible to directly
quantify ionicity via the Nernst−Einstein equation, confirming
the validity of the adjusted Walden plot approach as well.163
NMR spectroscopy is another tool used in the study of
proton transfer in protic ionic liquids.164,150,153,165 In
imidazolium PILs the chemical shift of the protons attached
to the nitrogen atom of imidazolium cation and imide anions
were used by Watanabe’s group.153 In another example, Burrell
and co-workers studied 15N NMR spectra of a series of PAILs
resulting from eight amine bases and six Brönsted acids.164 In
this study it was possible to distinguish between neutral and
ionized amine bases (ammonia vs ammonium-type ion), which
indicated that the protic ionic liquids were completely ionized
when made as a stoichiometric mixture. However, a Walden
plot comparison of fluidity and molar conductivity indicated
that the majority of PAILs had a much lower conductivity than
predicted by viscosity, unless the base contained excess proton-
donating groups. This disparity is indicative of protic ionic
molecules forming neutral aggregates or non-Newtonian fluid
hydrogen-bonded networks with a secondary Grotthuss
proton-hopping mechanism arising from polyprotic bases.164
In a recent development Moreira et al. reported the preparation
of 28 PAILs from active pharmaceutical ingredients and their
quantitative determinations of the degree of ionicity by 1H
NMR in DMSO-d6 solutions.166
3.2. Protic Acidic Ionic Liquids with Acidic Hydrogens on
Anion
When the donating proton is located in the anion fragment of
the acidic ionic liquid, these anions are generally derived from a
polybasic acid. The common acids used in PAILs are dibasic
sulfuric acid (H2SO4) and tribasic phosphoric acid (H3PO4);
replacement of all the hydrogens by ionic liquid cations forms
neutral ionic liquids if there are no acidic hydrogens on the
cation. However, if all the hydrogens are not replaced in the
anions, PAILs with proton donor anions are formed.
For example 1-butyl-3-methylimidazolium hydrogensulfate
can be prepared by reacting 1-butyl-3-methylimidazolium
chloride with one equivalent of sulfuric acid and removal of
volatile HCl to drive the reaction to produce the protic acidic
ionic liquid as shown in Figure 6. In addition 1-butyl-3-methyl-
Figure 6. Synthesis of Brönsted acidic ionic liquids with proton donor
anions.
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Figure 7. Protic acidic ionic liquids with acidic hydrogens on anion.
imidazolium hydrogensulfate ionic liquid has been prepared by
using sodium bisulfate in place of concentrated sulfuric acid as
well under microwave irradiation conditions with significantly
reduced reaction times.167
Some selected examples for protic acidic ionic liquids with
acidic hydrogens on the anion are dialkylimidazolium hydro-
gensulfate,168−171 dialkylimidazolium dihydrogen phosphate,170
and maleic and fumaric acid anions derived PAILs. A selected
sample of this type of Brönsted acidic ionic liquids is shown in
Figure 7.
3.3. Protic Acidic Ionic Liquids with Acidic Hydrogens on
Cation and Anion
There are protic ionic liquids with H+ on the cation as well as
on the anion such as diethylmethylammonium hydrogensulfate
[(C2)2C1HN][HSO4] described by Watanabe and co-workers
for prospective use as a fuel cell electrolyte.172 These are easier
to prepare by partial neutralization of a polybasic acid with an
organic base and some common examples are shown in Figure
8.
Figure 8. Protic ionic liquids with acidic hydrogens on cation and
anion.
3.4. Brönsted Acidic Ionic Liquids with Acidic Hydrogens
on a Functional Group
The fourth group of Brönsted acidic ionic liquids is the AILs
with an acidic functional group tethered to the ionic core
structure. This group can be seen as a type of functionalized
ionic liquid as well. Forbes, Davis, and others first described the
preparation of this type of strongly acidic BAILS with a −SO3H
group tethered to an ionic group in 2002.173 Nevertheless, The
synthetic approach used to assemble the zwitterionic precursors
to these acidic IL was reported by Yoshizawa et al. 2001.174
They synthesized a series of imidazolium cations containing
covalently bound anionic sites, such as sulfonate or sulfonamide
groups. These zwitterionic imidazolium salts were found to
form molten salts just like ordinary imidazolium salts. The acid
group can be attached to the ionic core directly or via a carbon
chain or a ring system. There are several methods of making
this type of BAILs. One widely used approach is the sultone
method; by which −SO3H functionalized ILs with C3 and C4
Figure 9. Two methods of preparation of −SO3H functionalized BAILs.
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tethers are easily prepared using propyl or butylsultones as
shown in the first reaction in Figure 9. In the first step alkyl
imidazole reacts with sultone to give a zwitterionic salt, which
can be treated with a Brönsted acid like HCl or HBr to give the
desired BAIL.175,176,173 Another method that has attracted
recent attention is the sulfonation of an aromatic system in the
neutral ionic liquid as shown in the second reaction in Figure
9.177 The carboxylic acid functionalized acidic ionic liquids are
generally synthesized via the corresponding carboxylic acid
esters.178
A wide variation in ionic core structures and multiple acidic
group containing BAILs are known, and some common
examples are shown in Figure 10.
3.5. Brö nsted Acidic Ionic Liquids with Acidic Hydrogens
on Functional Groups and on an Anion or Cation
The fifth type of BAILs can have two or more H+ on the acidic
functional groups and on the anion or cation. There are a
number of routes to synthesize this type of BAILs with multiple
acidic sites as shown in Figure 11. The aryl sulfonic acid ionic
liquid is prepared by direct sulfonation of the aromatic ring in
N-benzyl methylimidazolium chloride.177 In the second
reaction i‑butylamine is converted to BAILs in two steps
using sultones.179 Meng and co-workers has extended this
technique to produce a series of BAILs with multiple H+ on
−SO3H and nitrogens.179 The third reaction is the synthesis of
a caffeine based Brönsted acidic ionic liquid with a −SO3H
group and an acidic anion.180 The anion exchange with
polybasic acids such as H2SO4 and H3PO4 is also a valuable
technique in introducing acidic anions in these BAILs.181,182
A selected sample of Brönsted acidic ionic liquids with H+ on
acidic functional groups and on the anion or cation is shown in
Figure 12. Butylsulfonic-1,1,3,3-tetramethylguanidinium triflate
is an example of a BAIL with an acidic functional group and H+
on the cation.183 In addition acidic ionic liquids with several
acidic H+ on multiple locations are also known. For example,
N,N′,N″,N‴-tetrapropyl sulfonic hexamethylenetetramine tetra-
hydrosulfate is a BAIL with eight acidic hydrogens.184 The
acidic ionic liquid (4-butylsulfonic)tris(4-phenylsulfonic)-
phosphonium hydrogensulfate is another example. This highly
decorated molecule was described as a catalyst by Shaterian and
co-workers and is an example of a BAIL with three different
types of acidic protons.185
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Figure 10. Brönsted acidic ionic liquids with acidic hydrogen containing functional groups attached to the cation.
Figure 11. Synthesis of Brönsted acidic ionic liquids with acidic
hydrogens on functional group as well as on cation/anion.177
4. BRÖ NSTED-LEWIS ACIDIC IONIC LIQUIDS
The group of acidic ionic liquids with both Brönsted and Lewis
acidic characteristics in the same molecule is known as duel-
functionalized ionic liquids as well and is a relatively smaller
class. This type of AILs is particularly useful as catalysts as some
catalytic processes require both types of acidities in one or
more steps of the reaction. Synthesis and applications of
Brönsted-Lewis acidic ionic liquids have been reviewed in a
short review of 37 references in 2012.186
Examples for Brönsted−Lewis acidic ionic liquids of N-
methylpyrrolidonium zinc chloride [C1HPyrr][ZnCl3],187
Figure 12. Brönsted acidic ionic liquids with acidic hydrogens on functional groups as well as on cation/anion.
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[(HSO3)3C3C1im][(1/2.Zn)SO4],188 [(HSO3)4C4C1im][(1/
2.Fe)SO4],189 [(HSO3)3C3C1im][ZnCl3],190,191
[(HSO3)3C3(C2)3N][FeCl4],192 [(C2)3N][AlCl4],192,193 and
some of the structures are shown in Figure 13.
Figure 13. Brönsted−Lewis acidic ionic liquids.
Al, Zn, and Fe are the common Lewis acids used in
Brö nsted−Lewis acidic ionic liquids.194 However, Cu(1)
containing ionic liquids were also reported recently,195 where
a series of Brönsted−Lewis acidic Ionic liquids were prepared
by changing the Cu to BAIL mole ratio. In this method
[(HSO3)3C3C1im][HSO4] and CuO were mixed in distilled
water in the desired ratio, the solution was then stirred
continuously for about 2 h at 308 K and dried in vacuum to
produce a series of ILs with formulas such as
[(HSO3)3C3C1im][(1/2Cu2+)SO42−] and [(HSO3)3C3C1im]-
[(1/2H+.1/4Cu2+)SO42−].195 These task specific Brönsted−
Lewis acidic ionic liquids are known in various applications
including catalysis196−198 and desulfurization of diesel fuel.187
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Chemical Reviews
Spectroscopic methods can provide the Lewis acidity in
Brönsted−Lewis acidic ionic liquids. In one example Li and co-
workers proved the Lewis acidity of [(HSO3)4C4C1im][Fe-
(SO4)3.HSO4] by using IR spectroscopy.189 They used the
weak Lewis base acetonitrile as the probe, and the changes in
acetonitrile IR peaks at 1000−1600 and 2200−2400 cm−1 were
utilized to measure the Lewis acidity of the Brönsted−Lewis
AIL.189
5. POLYMERIC ACIDIC IONIC LIQUIDS
Polymeric acidic ionic liquids are an emerging subgroup in
AILs, which can combine all three: acidic, ionic liquid and
polymer properties to a single material. The swift progress and
explosive growth in polymeric ionic liquids area is reflected by
the large body of recent publications and some recent
reviews199−205 and particularly the imidazolium-based poly-
meric acidic ionic liquids are discussed in two recent dedicated
reviews206,207 justifying the importance of these polymers.
Polymeric acidic ionic liquids with ionic liquid and acid groups
as pendant group in a polymer chain are the most common
type. There are two basic synthetic approaches for assembling
this type of materials. These two methods are grafting the acidic
ionic liquid groups on to an existing polymer and polymer-
ization of an ionic liquid or AIL precursor.
5.1. Acidic Ionic Liquid Groups Grafted onto an Existing
Polymer
A handful of examples of this type is known, which includes;
immobilization of imidazolium - HSO4 on to a polymeric
support based on calix[4]resorcinarene,208 carboxyl function-
alized dication imidazolium-based ionic liquids209 and immobi-
lization of pyridinium propanesulfonic acid catalyst on
polychlorostyrene spheres.210
5.2. Polymerization of an Acidic Ionic Liquid Monomer
Polymerization of an acidic ionic liquid monomer or a
precursor is a more widely investigated approach. The general
examples include: imidazolium −SO3H heteropolyanion,211−215
poly(4-vinylpyridine),216−219 copolymerization of acidic ionic
liquid oligomers and divinylbenzene (DVB),220 polymerization
of 2-acrylamido-2-methyl-1-propanesulfonic acid salt of butyl-
amine,221 and resorcinol-formaldehyde222 based polymeric
acidic ionic liquids. Some of the common examples are
shown in Figure 14.
Figure 14. Some common polymeric acidic ionic liquids prepared by
polymerization of an acidic ionic liquid monomer.
In one example, Leng and co-workers reported the synthesis
of a −SO3H functionalized heteropolyanion containing
polymeric acidic ionic liquid by polymerization of the
zwitterionic monomer as shown in Figure 15.211 In addition
they used the new polymer as a heterogeneous catalyst for an
esterification reaction.211
The photopolymerization of acidic ionic liquid components
has been used in the fabrication of nanostructured proton-
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Figure 15. Synthesis of a polymeric acidic ionic liquid with acidic ionic
liquid as pendent groups.211
conductive films.223 In this approach ionic liquid crystals with
hexagonal and lamellar phases were successfully fabricated by
self-assembly based on intermolecular electrostatic interactions.
The polymerizable amphiphilic zwitterions are formed by the
reaction of 3-(1-vinyl-3-imidazolio)propanesulfonate (VIPS)
with 4-dodecyl benzenesulfonic acid (DBSA).223
6. IMMOBILIZED ACIDIC IONIC LIQUIDS
Immobilization of acidic ionic liquids can be carried out on
soluble or insoluble supports. However, the most common
examples are in the area of using insoluble supports to produce
heterogeneous acid catalyst systems. In many cases these
heterogeneous catalysts showed enhanced size and positional
selectivity compared to homogeneous catalysts as the solid
support imposes a specially designed environment around the
catalytic site.75 In addition, the immobilization may prevent
molecular aggregation or bimolecular self-destruction reactions,
which leads to deactivation of the catalytic sites. The most
important advantage is the ease of separation of the supported
acidic ionic liquid from reactants and products for reuse. The
commonly used supports are silica, alumina, zeolites and
polystyrene type polymers. A 2014 review titled “The use of
supported acidic ionic liquids in organic synthesis” with 79
references summarizes the recent progress in both inorganic
and organic supported AILs in catalysis applications.75
6.1. Immobilized on Inorganic Supports
Silica is the most widely used, convenient, and acid stable solid
support for BAILs, although there are a few examples in use of
zeolites and metal organic frameworks as well.224 There are
three basic techniques of immobilization, which involve grafting
of catalyst on to a silica surface, synthesis of silica material by
sol−gel formation, and adsorption on the solid surface. In 2010,
Amarasekara and Owereh reported the grafting of the
imidazolium propylsulfonic acid BAIL moiety onto a silica
surface in two steps by using chloropropyl silica as shown in
Figure 16.225 In addition this silica supported acid catalyst was
shown to be effective in the hydrolysis of cellulose (DP ≈ 450)
dissolved in 1-n-butyl-3-methylimidazolium chloride at 70 °C,
producing glucose and total reducing sugars in 26 and 67%
yields, respectively.225
Grafting the BAIL on to a silica surface using a longer carbon
chain allows easier access to the acidic function. Yokoyama et
al. grafted the BAIL group on to 3-mercaptopropyltrimethox-
ysilane modified silica gel by a free radical coupling reaction and
this catalyst was used for the esterification and nitration of
aromatic compounds.226 Similar BAIL catalysts have been used
in the esterification of oleic acid,227 synthesis of bis(indolyl)-
methanes,228 conjugate addition of indoles,229 and thioacetal-
ization of carbonyl compounds in water.230
Another common technique of immobilization of a catalyst
on silica is sol−gel synthesis by hydrolysis of a mixture of
silicates like tetraethyl orthosilicate (TEOS), and a silicate with
covalently linked catalytic function. This method has been
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Chemical Reviews
Figure 16. Synthesis of sulfonic acid functionalized acidic ionic liquid modified silica catalysts by grafting method.
successfully applied for the immobilization of acidic ionic
liquids. For example Miao and co-workers immobilized 1-(3-
propylsulfonic) imidazolium hydrogensulfate on silica−gel
using tetraethyl orthosilicate as the primary silica source as
shown in Figure 17.231 Selected examples of immobilizations of
AILs on inorganic supports and catalytic applications of the
immobilized AILs are shown in Table 2.
Figure 17. Synthesis of sulfonic acid functionalized acidic ionic liquid
modified silica catalyst by sol−gel synthesis method.231
Immobilization by adsorption or entrapment in an inorganic
support is another approach of immobilization of a catalyst,
which has been applied to AILs as well.281 Marr and co-workers
prepared a catalyst with (3-propylsulfonic)-trimethylammo-
nium type ionic liquid [(HSO3)3C3(C2)3N] ][NTf2] entrapped
within silica gel. This silica gel containing functionalized acidic
ionic liquid was used as a recyclable liquid phase catalyst for the
dehydration of rac-1-phenyl ethanol. Furthermore, hot filtration
tests showed that the activity was within the gel.281
6.2. Immobilized on Organic Supports
Acidic ionic liquid immobilized on organic polymeric structures
are also known. Polystyrene immobilized acidic ionic liquids are
generally prepared by copolymerization of a mixture of a BAIL
attached vinylbenzene and divinylbenzene as shown in Figure
18.282
The polystyrene based systems are the most widely used
organic supports, in addition poly(vinylpyridine)216 and
melamine resins283 have also been used as solid supports for
AILs. The recent examples of immobilization on organic
supports are listed in Table 3.
7. PHYSICAL PROPERTIES OF ACIDIC IONIC LIQUIDS
7.1. Solubility, Density, Viscosity, and Related Properties
Interest in physical properties of AILs has seen a rapid growth
as the applications have widened in the last 5−6 years. Wang
and co-workers studied the solubilities of benzothiazolium
acidic ionic liquids in common alcohols (methanol, ethanol, 1-
propanol, 2-propanol, 1-butanol, and 2-methyl-1-propanol) at
temperatures 253−384 K using a static equilibrium method
under atmospheric pressure.303 The modified Apelblat equation
and λh equation were employed to correlate the experimental
data with good agreement. It was interesting to find that the
solubilities of some ILs in alcohols were with “temperature-
sensitive” properties. The solubility is related to the polarity and
molecular structures of the solvent, as well as the strength of
hydrogen bonding between alcohols and anionic groups of ILs.
During these studies the dissolution enthalpy and entropy of
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ILs were calculated by using the van’t Hoff equation. This study
provides some useful information for further research and
applications of AILs.303
In 2014 the physical propertiesdensity, viscosity, molecular
volume, standard entropy, thermal expansion coefficient, and
crystal energyof four common Brönsted acidic ILs, 1-(3-
propylsulfonic)-3-methylimidazolium hydrogensulfate
[(HSO3)3C3C1im][HSO4], 1-(4-butylsulfonic)-3-methylimida-
zolium hydrogensulfate [(HSO3)4C4C1im][HSO4], 1-(3-pro-
pylsulfonic)-3-butylimidazolium hydrogensulfate
[(HSO3)3C3C4im][HSO4], and 1-(4-butylsulfonic)-3-butylimi-
dazolium hydrogensulfate [(HSO3)4C4C4im][HSO4], were
reported by Muhammad and co-workers.304 The density and
viscosity of these ILs are shown in Table 4, whereas molecular
volume Vm, standard entropy S0, thermal expansion coefficient
(αp) and crystal energy UPOT are shown in Table 5.
Standard entropy S0 was calculated using the equation
S 0 = 1246.5(Vm) + 29.5
where Vm is the molecular volume in nm3 and S0 is the standard
entropy in J K−1 mol−1. Lattice energy (UPOT) is reflected by
the strength of the interactions between its ions. This was
calculated using the following equation based on the Glasser
theory.305
UPOT = 1981.2(ρ /M) + 103.8
The thermal expansion coefficient (αp) values were
calculated using the equation304 αp = −A1/(A0 + A1T) where
A0 and A1 are the fitting parameters that have been determined
from the plot between density and temperature, while T is the
absolute temperature. The thermal expansion coefficient values
reflected the free volume of ionic liquid; that is, higher thermal
coefficient values correspond to higher free volume of ionic
liquid, similar to other types of imidazolium-based ILs.306,307 It
is interesting to note that relatively low values of thermal
expansion coefficients were obtained for these ILs, and this
could be due to more compact spatial molecular structures of
the ILs.
Viscosity and particularly the temperature dependence of the
viscosity or rheology properties of protic ionic liquids is an area
of particular interest as these measurements provides
information regarding H-bonding network in the
PAILs.308−311 Atkin and co-workers studied the rheological
properties of a series of protic ionic liquids, ethylammonium
nitrate [C 2 (H) 2 N][NO 3 ], propylammonium nitrate
[C3(H)2N][NO3], ethanol ammonium nitrate [HO2C2(H)2N]-
[NO3], ethylammonium formate [C2(H)2N][HCO2], and
dimethylethylammonium formate [C2(C1) 2H3N][HCO2].
They interpreted the viscosity data by considering the effects
of both the H-bond network and the solvophobic nanostruc-
ture of the liquids.309 At 20 °C, [C2(H)2N][NO3] has the
highest zero shear viscosity of 156.1 mPa s, followed by
[C3(H)2N][NO3]. They found that primary ammonium ILs
behave as Newtonian fluids at low shear rates but shear thin at
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 Table 2. Selected Examples of Immobilizations of AILs on Inorganic Supports and Their Catalytic Applications
acidic ionic liquid support application refs
1-benzyl-3-methylimidazolium hydrogensulfate silica esterification of fatty acids 232
propylsulfonic acid imidazolium silica hydrolysis of cellulose in water, N-Boc protection of amines 233,234
propylsulfonic acid imidazolium hydrogensulfate nanosilica synthesis of indazolophthalazine-triones and bis-indazolophthalazine-triones 235
methylimidazolium hydrogen sulfate silica esterification 236
Chemical Reviews

3-propylsulfonic methylimidazolium silica adsorption of Cr6+ and Cr3+ 237

hydrogensulfate
1-methyl-3-propyl-imidazolium hydrogensulfate. amorphous silica preparation of 1-(benzothiazolylamino)phenylmethyl-2-naphthols 238
propylsulfonic acid imidazolium hydrogensulfate surface of Fe3O4@SiO2 esterification of oleic acid with short-chain alcohols and trans-esterification of soybean oil. 239
N-propyl-2-pyrrolidonium hydrogen sulfate nanosized silica-coated magnetite diazotization-iodination of aromatic amines 240
1-methyl-3-propyl-imidazolium hydrogen sulfate rice husk ash amorphous silica N-formylation of amines using formic acid 241
propylsulfonic acid imidazolium hydrogen silica benzaldehyde ethylene glycol acetal synthesis and rape seed oil biodiesel synthesis 242
sulfate
1-methyl-3-propyl-imidazolium hydrogen sulfate nanoporous silica SBA-15 Knoevenagel−Michael synthesis of tetrahydrochromenes and hexahydroquinoline carboxylates 243
1-butylsulfonic imidazolium cobalt ferrite nanoparticles esterification of oleic acid with straight-chain alcohols 244
trifluoromethanesulfonate embedded in silica
propylsulfonic acid imidazolium hydrogen silica tetraethoxysilane (TEOS) benzaldehyde ethane diol acetal and n-butyl acetate synthesis 245,246
sulfate as silica source
1-(4-butylsulfonic)-3-propylimidazolium silica esterification and acetalization 247
hydrogen sulfate
1-(4-butylsulfonic)-3-propylimidazolium silica synthesis of amidoalkyl naphthols 248
hydrogen sulfate
1-(4-butylsulfonic)-3-vinylimidazolium silica hydrogenation of nitrobenzene to p-aminophenol 249

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1-(4-butylsulfonic)-3-methylimidazolium silica esterification of hexanoic acid with ethanol 250
hydrogen sulfate
1-(3-propylsulfonic)-3-vinylimidazolium silica esterification of acetic acid with n-butyl alcohol 251
hydrogen sulfate
1-(4-butylsulfonic)-3-allylimidazolium silica dehydration of fructose to HMF 252
trifluoromethanesulfonate
1-butylsulfonic-3-methylimidazolium - impregnation on silica and Friedel−Crafts alkylation of benzene, cumene, toluene, naphthalene, with alkenes 253−256
aluminum chloride MCM-41
1-(3-propylsulfonic)-3-vinylimidazolium silica with meso and macropores Baeyer−Villiger oxidation 257
hydrogen sulfate
1-butyl-3-methylimidazolium aluminum silica trimerization of isobutene 258
chloride
1-butyl-3-methylimidazolium iron(III) chloride silica and MCM-41 Friedel−Crafts acylation 259
triethylammonium aluminum chloride 5 Å molecular sieves reaction of epoxypropane with POCl3 260
tetraalkylammonium or pyridinium chloride - silica synthesis of 3-methyl-3-buten-1-ol by Prins reaction 261
tin(IV) chloride
1-propyl-3-methylimidazolium aluminum silica and MCM-41 benzylation of aromatic substrates 262
chloride
butylsulfonic pyridinium hydrogen sulfate silica synthesis of 2-aryl-2,3-dihydroquinazolin-4(1H)-ones 263,264
1-(4-butylsulfonic)-3-methylimidazolium silica oligomerization of isobutene 265,266
hydrogen sulfate and triflate
1-(3-propylsulfonic)-3-methylimidazolium silica synthesis of pyrano[3,2-b]indole derivatives, 2,9-dihydro-9-methyl-2-oxo-4-aryl-1H-pyrido[2,3-b]indole-3-carbonitrile 267−272
hydrogen sulfate compounds and 5-amino-7-aryl-6-cyano-4H -pyrano[3,2-b ]pyrroles
1-(3-[ropylsulfonic)-3-methylimidazolium biginelli synthesis of 3,4-dihydropyrimidin-2(1H)-ones/thiones 273
Review

magnetic Fe3O4 nanoparticles

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hydrogen sulfate with a silica shell
Chemical Reviews Review

high shear. In addition they fit the Vogel−Fulcher−Tammann

274,275

279,280
refs model, which revealed that nanostructure is not affected

276
244

277

278
appreciably by temperature and that all the ILs studied is of
intermediate fragility. The rheology of binary mixtures of these
ILs were also analyzed and used to demonstrate fundamental
differences in the interactions of cations and anions.309
Broadband dielectric spectroscopy and pressure−temper-
ature−volume methods are other methods used in physico-
chemical studies on acidic ionic liquids.311 These techniques
were employed to investigate the effect of hydrostatic pressure
on the conductivity relaxation time (τσ), both in the
supercooled and glassy states of protic ionic liquid lidocaine
hydrochloride monohydrate. Due to the decoupling between
the ion conductivity and structural dynamics, a change in
behavior of τσ(T) dependence (from Vogel−Fulcher−Tam-
ketalization of cyclohexanone with glycol, 1,2-propylene glycol and 1,3-butylene glycol

mann like to Arrhenius like behavior) was observed for

lidocaine HCl. This crossover is a manifestation of the liquid-
glass transition of lidocaine HCl. Additionally, Swiety-Pospiech
et al. analyzed the changes of conductivity relaxation times of
the AIL sample and found that compression enhances the
synthesis of 1H-pyrazol-5-ol derivatives and N-formylation of amines
application

decoupling of electrical conductivity from the structural

relaxation of these protic ionic liquids.311
7.2. Acidity
Many research groups have studied acidity properties as this
acetal formation of benzaldehyde with ethylene glycol
esterification of oleic acid with straight-chain alcohols

character is critical in many applications.312 The acid

dissociation constant measurement is a one key experiment.
This includes the studies on effects of alkyl chain lengths,
solvents on thermodynamic dissociation constants.313,178 The
acidity of BAILs can be measured using UV−visible
absorption of ethane and ethylene.

spectrophotometry by means of a basic indicator, such as 4-

nitroaniline in water. Hammett acidity function H0 can be
synthesis of benzoxanthenes

calculated using the following equation. The [I]/[IH+] (I

represents indicator) ratio can be determined from the
absorbance measured before and after the addition of BAILs.
⎡ (I) ⎤
H0 = pK (I)aq + log⎢ ⎥
⎣ (IH+) ⎦
In one illustration Xing and co-workers have investigated the
Brönsted acidities of sulfonic acid-functionalized BAILs with
nanoporous Na+-montmorillonite
silica-coated Fe3O4 nanoparticles

pyridinium cations.314 For these BAILs the Hammett function

values are between −1.5 and −3.6 at 110 °C as shown in Table
cobalt ferrite nanoparticles

6. The absorption spectra of 0.025 mg/mL 2,4-dichloro-6-

embedded in silica
support

nitroaniline (A) and [(HSO3)3C3pyr][BF4] were used in the

Fe3O4 nanoparticles

calculation of H0 as shown in Figure 19. Additionally they

MOR zeolite

found that the minimum-energy geometries of sulfonic acid-

MCM-22

functionalized BAILs manifest in anions that have strong

clay

interactions with the sulfonic acid proton. It is accepted that in

addition to the alkyl sulfonic acid group, the anion is likely to
serve as an available acid site. Hence the acidities and catalytic
1-propyl-3-methylimidazolium hydrogen sulfate

activities of −SO3H functionalized ILs depend on the kinds of

anions as well.314
1-(3-propylsulfonic)-3-methylimidazolium

1-(4-butylsulfonic)-3-methylimidazolium

1-(4-butylsulfonic)-3-methylimidazolium

Kang and co-workers have studied Brönsted−Lewis acidic

1-(4-butylsulfonic)-3-allylimidazolium
tolylsulfonic phosphonium chloride

ionic liquids [(HSO3)4C4C1im][Cl-.xZnCl2] with different

acidic ionic liquid

molar fractions of zinc chloride using Hammett method

trifluoromethanesulfonate

combined with UV−visible spectroscopy. In this work the

Table 2. continued

catalytic performance of [(HSO3)4C4C1im][Cl-.xZnCl2] for the

synthesis of methylene diphenyl dimethyl carbamate (MDC)
hydrogen sulfate

hydrogen sulfate

hydrogen sulfate

from methyl N-phenyl carbamate (MPC) and formaldehyde

(HCHO) was corelated to the ZnCl2 content. The results
showed that [(HSO3)4C4C1im][Cl.0.7ZnCl2] had the highest
catalytic activity.191 In another study the ionicity of −SO3H
functionalized ionic liquids [(HSO3)3C3iC4(H)2N][HSO4] and
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Figure 18. Synthesis of a polystyrene immobilized Brönsted acidic ionic liquid catalyst.

Table 3. Selected Examples of Immobilizations of AILs on Organic Supports and Their Catalytic Applications
acidic ionic liquid support/technique application refs
methylimidazolium iron(III)tetrachloride polystyrene reactions of aziridines/propargyl amines 130
with CO2
carboxyl-isobutyl-imidazolium bromide polystyrene cycloaddition reaction of CO2 with epoxides 284
1-butyl-4-vinylpyridinium chloroaluminate, 1-butyl-3- polymerization to branched polyethylene Diels−Alder reaction of cyclopentadiene 285
vinylimidazolium chloroaluminate, and 1-ethyl-3- with methyl methacrylate
vinylimidazolium chloroaluminate
1-butyl-3-vinylimidazolium chlorogallate copolymerization with styrene acetalization of carbonyl compounds with 286
methanol
1-butyl-3-vinylimidazolium bromozincate and 1-ethyl-3- polymerization coupling reactions of alkylene oxide and 287
vinylimidazolium bromozincate CO2 to produce alkylene carbonates
288
1-N-ferrocenyl methylimidazolium hydrogensulfate Merrifield resin homoallylic alcohols from Ar−CHO and
allyltrimethylsilane
1-(3-propylsulfonic) imidazolium hydrogensulfate grafted to chloromethylated polystyrene esterification
(4-butylsulfonic)-pyridinium hydrogensulfate propyl sulfonation of poly(4-vinylpyridine) synthesis of 4,4′-(arylmethylene)bis(3- 289,219,290
methyl-1-phenyl-1H-pyrazol-5-ols)
(4-butylsulfonic)-melaminium hydrogensulfate melamine-formaldehyde resin with 1,4- acetal formation with diols 283
butanesulfonate
(3-propylsulfonic)-pyridinium [PW12O40] reaction of 4-vinylpyridine with 1,3-propane sultone, 2,3-dihydro-4(1H)-quinazolinones 216
followed by the polymerization and the addition
of the heteropolyacid.
[1-butyl-3-(3-trimethoxypropyl)- imidazolium grafted on cellulose hydroxylated pyridines 291
hydrogensulfate
1-(3-propylsulfonic) imidazolium dihydrogen phosphate polystyrene biodiesel from vegetable oil 220
1-(3-propylsulfonic) imidazolium hydrogensulfate polystyrene esterification of n-BuOH with acetic acid. 292−296,212
Nitration of toluene with HNO3.
Oxidation of benzothiophene
1-methylimidazolium aluminum chloride polystyrene Knoevenagel condensation of aromatic and 297,298
aliphatic aldehydes with ethyl
cyanoacetate.
1-(3-propylsulfonic) imidazolium hydrogensulfate polystyrene grafted silica gel esterification 299
1-(4-autylsulfonic) imidazolium hydrogensulfate polystyrene Hantzsch 1,4-dihydropyridine synthesis 300
alkyl imidazolium hydrogensulfate poly calix[4]resorcinarene condensation of amides with aldehydes to 208
give bisamides
1-(3-propylsulfonic) imidazolium dihydrogen phosphate polystyrene biodiesel from vegetable oil 220
1-(3-butylsulfonic)-3-vinylimidazolium triflate and 1-(3- copolymerization with styrene acetalization of aldehydes 301,302
propylsulfonic)-3- vinylimidazolium hydrogensulfate

Table 4. Density and Viscosity Data for Some Common Table 5. Molecular Volume, Vm, Crystal Energy (UPOT),
BAILs (at 20 °C and p = 0.1 MPa)a304 Thermal Expansion Coefficient (αp), and Standard Entropy
(S0) of Selected BAILs at 20 °C304
BAIL density (ρ) g/cm3 viscosity (η) mPa·s
3
[(HSO3) C3C1im][HSO4] 1.5017 1296 Vm UPOT αp 104/ S0
BAIL (nm3) (kJ mol−1) (K−1) (J K−1 mol−1)
[(HSO3)4C4C1im][HSO4] 1.4647 1427
[(HSO3)3C3C4im][HSO4] 1.3469 1000 [(HSO3)3C3C1im] 0.333 442.19 3.81 445.03
[HSO4]
[(HSO3)4C4C4im][HSO4] 1.3611 1592
[(HSO3)4C4C1im] 0.357 434.24 3.91 474.95
a
Standard uncertainty u is u(T) = 0.01 °C and the combined expanded [HSO4]
uncertainty is uc(ρ) = 3 × 10−4 g/cm3, uc(η) = 0.4% mPa·s (level of [(HSO3)3C3C4im] 0.423 416.21 4.21 557.21
confidence = 0.95).304 [HSO4]
[(HSO3)4C4C4im] 0.436 413.12 4.25 573.42
[HSO4]
[(HSO3)4C4iC4(H)2N][HSO4] have been assessed by the
product of molar conductivity and viscosity.179 probe.315 The Gutmann acceptor no. (AN), which is a
In addition to UV−vis spectroscopic methods, NMR can also quantitative measure of Lewis acidity, has also been estimated
be used in the determination of acidities of ionic liquids. using the 31P NMR chemical shift of a probe molecule
Welton et al. introduced this technique as a quick, simple, triethylphosphine oxide, for a range of chlorometallate(III)
robust method to measure acidity in ionic liquid systems by the ionic liquids based on Group 13 metals (aluminum(III),
use of the NMR-probe mesityl oxide. Acidity corresponding to gallium(III), and indium(III).316
a Hammett acidity of 1−9 could be measured reliably using this There are attempts to correlate calculated H0 values of BAILs
technique, a range that vastly exceeds that of any single UV−vis with catalysis activities in chemical reactions such as, Pechmann
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Table 6. H0 Values of the Sulfonic Acid-Functionalized 7.3. Thermo-Physical Properties

BAILs with Different Anions at 110 °C314 In 2011, Amarasekara and Owereh first reported the thermal
sulfonic acid functionalized water content of [I] [HI] decomposition onset temperatures for a total of 24
BAIL BAIL (%) (%) (%) H0 methylimidazolium, triethanolammonium, and pyridinium
[(HSO3)3C3pyr][BF4] 5.7 33 67 −3.6a type sulfonic acid group functionalized Brönsted acidic ionic
[(HSO3)3C3pyr][HSO4] 5.0 51 49 −3.3a liquids with Cl−, Br−, SO42−, PO43−, BF4−, CH3CO2−, and
[(HSO3)3C3pyr][p-TSA] 6.1 36 64 −2.1b CH3SO3− anions.331 Thermal stabilities of these sulfonic acid
[(HSO3)3C3pyr][H2PO4] 6.0 81 19 −1.2b group functionalized ionic liquids decreased in the order
[(HSO3)3C3pyr][ H2PO4] 2.0 65 35 −1.5b methylimidazolium > triethanolammonium > pyridinium. The
a
Indicator: 2,4-dichloro-6-nitroaniline. b
Indicator: 2,5-dichloro-4- methylimidazolium, pyridinium, and triethanolammonium ionic
nitroaniline. liquids investigated showed decomposition onset temperatures
(air) in the 213−353, 167−240, and 230−307 °C ranges,
respectively. Additionally, they found that the decomposition
temperatures of these ionic liquids are highly dependent on the
nature of the anion.331 The thermophysical properties of acidic
ionic liquid 1-(4-butylsulfonic)-3-methylimidazolium chloride
[(HSO3)4C4C1im][Cl] has been compared with that of the
corresponding neutral ionic liquid butylmethylimidazolium
chloride [C4C1im][Cl] as shown in Figure 20. The acidic
ionic liquid decomposed in three steps with DTG peaks
centered at 269, 373, and 387, whereas the neutral [C4C1im]-
[Cl] decomposed in one step.331

Figure 19. Absorption spectra of 0.025 mg/mL 2,4-dichloro-6-

nitroaniline before (A) and after (B) addition of [(HSO3)3C3pyr]-
[BF4]. Reprinted with permission from ref 314. Copyright 2007
Elsevier.

condensation,317 hydration of alkynes,177 Fischer indole

synthesis,318 coupling of epoxides and CO2,319 alcoholysis of
furfural alcohol to alkyl levulinates,320 esterification,321−324
fructone synthesis,325 2-phenylbenzimidazole synthesis,326
degradation of lignin model compounds,327 acetal synthesis328
and dehydration of fructose.329 In one instance H0 values of a
series of BAILs have been corelated to the yields and Figure 20. Thermogravimetric analysis (TG) and derivative
conversions in the synthesis of methylene diphenyl dimethyl thermogravimetric analysis (DTG) curves for 1-(4-butylsulfonic)-3-
carbamate (4,4′-MDC) from methyl N-phenyl carbamate methylimidazolium chloride [(HSO3)4C4C1im][Cl] and 1-butyl-3-
methylimidazolium chloride [C4C1im][Cl] under N2 atmosphere.331
(MPC) and formaldehyde (HCHO) as shown in Table 7.330 Reprinted with permission from ref 331. Copyright 2010, Springer.
These experiments show that CF3SO3 and HSO4 anion
containing BAILs with lower H0 values gives higher MPC
conversions and MDC yields. Later Muhammad and co-workers reported a comparison of
the thermal decomposition temperatures of Brönsted acidic ILs
Table 7. Corelation between Catalytic Activities of Ionic and their corresponding zwitterions of 1-(3-propylsulfonic)-3-
Liquids and Their H0 Values330 methylimidazolium chloride [(HSO3)3C3C1im][Cl], 1-(3-pro-
pylsulfonic)-3-butylimidazolium chloride [(HSO3)3C3C4im]-
sulfonic acid conversion of yield of selectivity [Cl], 1-(4-butylsulfonic)-3-methylimidazolium chloride
functionalized BAIL MPC (%) MDC (%) MDC/MPC H0 [(HSO3)4C4C1im][Cl], and 1-(4-butylsulfonic)-3-butylimida-
[(HSO3)4C4C1im] 54.9 61.6 55.8 −3.6 zolium chloride [(HSO3)4C4C4im][Cl].304
[CF3SO3] The effect of alkyl groups on thermal degradation and
[(HSO3)4C4C1im][ 60.3 42.7 34.3 −3.3 viscosity is a common theme in many studies on ILs.332 Santos
HSO4]
and co-workers studied several physicochemical properties
[(HSO3)4C4C1im][ 33.2 7.4 11.1 −0.8
p-TSA] including glass transition temperatures of a series of systems of
[(HSO3)4C4C1im] 34.3 4.6 6.7 −0.7 the type [C1Him][NTf2], [C2Him][NTf2], [1C12C1Him]-
[CH3SO3] [NTf2], and [1C42C13C1im][NTf2].333 They established a linear
[(HSO3)4C4C1im] 18.5 +0.9 correlation between the glass transition temperature Tg and the
[CF3 COO] alkyl chain size. It was found that the most viscous ILs
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Chemical Reviews
([1C1Him][NTf2], [1C2Him][NTf2], and [1C12C1Him][NTf2])
have an acidic N−H group in the imidazolium ring, which is in
agreement with the observed increase in energy barrier of flow.
The methylation in C-2 position as well as the N−H acidic
group in the imidazolium ring contributes to a significant
variation in the cation−anion interactions and their dynamics,
which is reflected in their charge distribution and polarizability
leading to a significant differentiation of the refractive indices,
surface tension, and heat capacities.333
7.4. Ionic Conductivity
Ionic conductivity of AILs in relation to structure is another
useful tool in extracting structural information.334−336 The self-
assembled ordered structures of AILs are known to have
improved conductivities as well.337 The energetics of transfer of
a proton from one member of the pair to the other is a
common approach applicable in protic ionic liquids.338 In a
recent investigation Wu and co-workers studied the ionic
conductivities of a series of protic ionic liquids based on
acetamide and Brönsted acids (HX, where X is CF3COO−,
CH 3 COO −, or HSO 4 − ). They found that the ionic
conductivities for most of the samples are between 10−3 and
10−1 S/m at room temperature. Acetamide trifluoroacetate with
acetamide: trifluoroacetic acid 1:1 mol ratio showed an ionic
conductivity of 0.25 S/m, and a viscosity of 10 cP at 25 °C.
Moreover, most of the AILs studied possessed relatively
moderate thermal stabilities (up to 106 °C for acetamide
trifluoroacetate) and a wide liquid range (down to −69 °C for
acetamide trifluoroacetate). The ionic conductivity properties
observed in this study may perhaps make these acetamide-
based PILs of interest as reaction media, catalysts in organic
synthesis, or as electrolytes in fuel cells.334
7.5. Spectroscopy
The NMR characterizations of acidic ionic liquids are reported
in some publications on synthesis and applications of AILs and
in most cases the NMR spectra are recorded in D2O or DMSO-
d6. In addition to the structural characterization, NMR
spectroscopy have been used in the determination of acidity
in ionic liquids,315,339 study AILs in aqueous environments,340
ion-pairing behavior,341 anion speciation by 119Sn342 and 27Al343
NMR spectroscopy. For instance Lewis and Brönsted acidic
species of chloroaluminate ILs have been investigated by 27Al
NMR spectroscopy. These experiments revealed that Lewis
acidity arises mainly from Al2Cl7−, having a chemical shift at
102 ppm in the 27Al NMR spectrum, while Brönsted acidity
arises from Al2Cl6OH− (chem. shift at 97 ppm). The peak at 94
ppm in the 27Al NMR spectrum is related to Al2Cl5O−.339 A
selected set of references for UV−vis, IR, and 1H and 13C
NMR, mass spectroscopy of common acidic ionic liquids are
shown in Table 8.
7.6. Miscellaneous Physical Properties
In addition to the physical properties discussed, a number of
other interesting characteristics of AILs have been explored in
recent years. These include studies on aggregation, crystal
structure, chiral recognition and some of these examples are
shown in Table 9.
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Review
Table 8. Selected Set of References for Spectroscopy of
Common Acidic Ionic Liquids
acidic ionic liquid type spectroscopy refs
1-(alkyl sulfonic)-3-alkylimidazolium and IR, 1H, 13C 344−350
imidazolium PAILs NMR, mass
pyridinium hydrogensulfate IR, 1H, 13C 351−353
NMR
alkyl sulfonic acid benzimidazolium IR, 1H, 13C 354
NMR
1,1′-disulfo-[2,2′-bipyridine]-1,1′-diium IR, 1H, 13C 355
chloride NMR
succinimidinium N-sulfonic acid IR, 1H, 13C 356,357
NMR
1
alkylsulfonic ammonium, [(C2)2H2N][OTf] H, 13C NMR 358−362
and [(C2)3HN][OAc]
8. COMPUTATIONAL STUDIES ON ACIDIC IONIC
LIQUIDS
8.1. Computational Studies on Acidity and Other Physical
Properties
Several research groups have used computational methods to
predict and explain acidity related parameters, hydrogen
bonding characteristics and molecular geometries of Lewis
and Brönsted acidic ionic liquids.376−378 Liu and co-workers
used density functional theory to study the −SO3H function-
alized acidic ionic liquid 1-(3-propylsulfonic)-3-methylimidazo-
lium hydrogen sulfate [(HSO3)3C3C1im][HSO4] and its
precursor zwitterion compound.379 These species were
optimized systematically by the DFT theory at B3LYP/6-
311++G** level, and their most stable geometries were
obtained. The calculation results indicated a great tendency
to form strong intramolecular hydrogen bonds in the
zwitterion, and this tendency was weakened in the cation,
which was the protonation product of the zwitterion. The
intramolecular hydrogen bonds and intermolecular hydrogen
bonds coexisted in the ionic liquid, and they played an
important role in the stability of the systems. The strongest
interaction in the ionic liquid was found between the anion and
the functional group. The transition state research and the
intrinsic reaction coordinate analysis of the hydrogen transfer
reaction showed that when the cation and the anion interacted
near the functional group by double O−H···O hydrogen bonds,
the ionic liquid was inclined to exist in a form of the zwitterion
and H2SO4.379 In addition the acidity in imidazolium
bromoalumanate LAILs have also been examined using DFT
methods.376
In a recent study dynamic simulation based on the ion pair
charge approach has been performed to investigate the
structural characteristic of −SO3H functionalized ILs in the
development of new proton conductive materials.380 In this
study Shan and co-workers found that there are significant
aggregations of sulfonic acid side chains due to strong
interactions between different sulfonic acid groups. Further-
more, they observed that after the introduction of a sulfonic
acid group to the side chain of the cation, the properties of the
anions have a remarkable influence on the preferential location
of anions in the interfacial region.380
8.2. Computational Studies on Acidic Ionic liquid Catalysis
There are a handful of cases where computational methods
have been used for explaining the mechanisms, product
distributions, and stabilities by computational methods in AIL
catalyzed reactions. These studies include 1-ethyl-3-methyl-
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Table 9. Miscellaneous Physical Properties Studies of Some Common Ionic Liquids
ionic liquid(s)
amines neutralized by bis(trifluoromethanesulfonic) amide, Alkanol amines neutralized by organic
acids, 1,8-diazabicyclo[5,4,0]undec-7-ene neutralized by Brönsted acids and [(C4)3HP][BF4]
decahydroisoquinoline neutralized by Brönsted acids
heterocyclic amines neutralized by trifluoroacetic acid
[Pyrr][HSO4] and [Pyrr][OTf]
[(HO2C2)H3N][C4−COO]
ephedrines neutralized by bis(trifluoromethanesulfonyl)amide and bis(pentafluoroethanesulfonyl)
amide
[(HO2C2)H3N][oleate]
[Hbim][Tfsa] (Tfsa= bis(trifluoromethanesulfonyl)amide)
N-(2-hydroxyethyl)piperazinium propionate
[(HO2C2)H3N][NO3]
[C2Him][OTf]
1-ethyl-2-butyl-benzimidazolium tetra-fluoroborate
imidazolium cation [C2C1im]+ and chloroaluminate (AlCl4 −
and Al2Cl7 −) catalyzed Diels−Alder cyclo-addition of methyl
acrylate to cyclopentadiene,381 removal of dibenzothiophene
and 4,6-dimethyldibenzothiophene from model diesel,382
glucose transformations, 383 extractive desulfurization in
[C4C1im][AlCl4],384 ether formation,385 and biodiesel syn-
thesis.386 In a recent development Li and co-workers reported a
DFT study on the mechanism for 1-(4-butylsulfonic)-3-
methylimidazolium hydrogen sulfate [(HSO3) 4C 4C 1im]-
[HSO4] catalyzed conversion of glucose into 5-hydroxyme-
thylfurfural. They found that the conversion may proceed via
two potential pathways and that throughout most elementary
steps; the cation of BAIL plays a substantial role, functioning as
a proton shuttle to promote the reaction. The chloride anion
interacts with the substrate and the acidic proton in the
imidazolium ring via H-bond, as well as provides a polar
environment together with the imidazolium cation to stabilize
intermediates and transition states. The calculated overall
barriers of the catalytic conversion along two potential
pathways are 32.9 and 31.0 kcal/mol respectively, which are
compatible with the observed catalytic performance of the AIL
under mild conditions (100 °C).387 The fixation of carbon
dioxide with epoxides catalyzed by a carboxylic acid function-
alized IL catalyst has also been investigated using computa-
tional methods. In this case, catalysis mechanism of 1-(2-
carboxyethyl)pyridinium-4-carboxylic acid bromide was ex-
plored using density functional theory techniques.388
9. APPLICATIONS OF ACIDIC IONIC LIQUIDS
9.1. Catalysis Applications
In acid catalysis there are typical Lewis acid catalyzed reactions
like Friedel−Crafts alkylation and Brönsted acid catalyzed
reactions like esterification. Lewis acid catalyzed reactions are
noticeable by electron transfer toward electron deficient Lewis
acid and formation of a charge separated complex. Brönsted
acid catalyzed reactions are marked by proton transfer, and in
these reactions proton transfer can make one reacting partner
more electrophilic. Then acid catalysis can occur in two
different ways: specific acid catalysis and general acid catalysis.
Specific-acid catalysis refers to a process in which the reaction
rate depends upon the specific acid in the solution. In most
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Review
physicochemical properties studied refs
temperature dependencies of density, viscosity, 363−366
conductivity, and electrochemical activity
ionicity and fragility 159
capacitance with a RuO2 electrode and energy 367
storage mechanisms
self-diffusion coefficients and conductivities 336
aggregation by 1H, and 13C NMR spectroscopy 368
chiral recognition 369
effect of temperature on density, speed of 370
sound, viscosity, and refractive index
proton conductivity by Raman and NMR 371
spectroscopy
molar volume, viscosity and electrical 372
conductivity
thermal conductivity 373
ion−ion association by molar conductivity 374
crystallographic structure by X-ray diffraction 375
analysis
cases the specific acid is the protonated form of the solvent in
which the reaction is being performed. General acid catalysis is
a system in which more than one species behaves as an acid.
Acidic ionic liquids are used in applications where they behave
as Lewis and Brönsted acids as well as in reactions involving
both mechanisms. In addition AILs are known in the form of
homogeneous and heterogeneous acid catalysts as well. In
numerous cases the substitution of a conventional acid with an
AIL has resulted in improvements in yield, turnover number
(TON), or turnover frequencies (TOF) and catalyst
recyclabilities, outperforming their traditional counterparts
when used in classical reactions.
9.1.1. Esterification and Saponification. Esterification
and saponification are industrially important and widely studied
acid catalyzed reactions. A fair number of researchers have
studied the possibility of substitution of classical acid catalysts
with AILs for these reactions.389 The biodiesel synthesis is in
fact a good example of saponification-esterification process;
however, biodiesel synthesis is presented as a separate subtopic
in this review as it is an extensively studied current application
that needs special attention. Therefore, only esterifications and
saponifications which are not directly related to biodiesel
production are covered in this section. Only about a dozen
examples are known in homogeneous catalysis area, however
some trans-esterification390,391 and considerable variations in
acidic ionic liquid types are known. For instance hydrophobic
1-(4-butylsulfonic)-3-octylimidazolium hydrogen sulfate
[(HSO3)4C4C8im][HSO4] has been used as an efficient catalyst
for esterification of oleic acid with methanol392 with excellent
results, and some selected examples from recent applications
are shown in Table 10. In addition to the homogeneous acid
catalysis, AILs have been used as supported heterogeneous
catalysts as well in esterification. In one example, a series of
polystyrene-supported 1-(3-propylsulfonic)-3-methylimidazo-
lium hydrogensulfate catalysts with different acidic ionic liquid
contents have been tested for esterification of n‑butyl alcohol
with acetic acid. In this study, the reactivity of the catalyst
increased with increasing [(HSO3)3C3C1im][HSO4] content,
and a 98% yield of n‑butyl acetate was obtained with the best
catalyst.292
9.1.2. Alkylation. Alkylation or the attachment of an alkyl
group can be achieved through electrophilic, nucleophilic and
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Table 10. Esterification and Saponification Using Acidic Ionic Liquid Catalysts
acidic ionic liquid catalyst(s) esterification/saponification reaction refs
[C6C1im][HSO4] oleic acid with lauryl alcohol in TX-100/cyclohexane 393
[(HSO3)4C4C1im][HSO4] oleic and caprylic acid with methyl alcohol 394,346
[(HSO3)4C4(CC)im][OTf] on magnetic mesoporous silica oleic acid with straight-chain alcohols 244
[(HSO3)4C4C1im][HSO4] n-butyric acid with methanol 324
[(HSO3)3C3C1im][HSO4] on silica acetic acid with ethanol, n-octanol, n-decanol 226
[(C2)3N][HSO4], [(C2)3N][H2PO4], [(C2)3N][OTs], [Bz(C2)2N][HSO4], [(C4)3N] acetic acid with 1-octanol 395
[HSO4], [(C8)3N][HSO4], [(C2)2HN][HSO4], and [(C2)2HN][H2PO4]
[(HSO3)3C3(CC)im][HSO4] on silica n-butanol and acetic acid 246
[(HSO3)3C3(C2)3N][HSO4], and [(HSO3)3C3(C2)3N][H2PO4] α-pinene with acetic acid 396
[(HSO3)4C4C1im][HSO4], [(HSO3)3C3pyr][HSO4], and [(HSO3)3C3(C2)3N] n-caproic, benzoic acid with 1-butanol, 1-octanol and iso-amyl 175
[HSO4] alcohol
[(HSO3)4C4C1im][OTf] acetic acid with 1-heptene 397
guanidinium tetrafluoroborate formic and butaric acids with alcohols 398
SO3H-functionalized IL polymer with heteropolyacid (HPA) acetic acid with n-butanol, ethylene glycol, dodecanol 211
polyoxometalate-based sulfonated ionic liquid palmitic acid with ethanol 399
choline chlorostanate, chlorozincate and chloroferrate phytosterols with fatty acids 400
−SO3H functionalized imidazolium BAILs acetic and benzoic acids with benzyl alcohol 321
[(HSO3)3C3C1im][HSO4], [(HSO3)3C3C1im][OTs], [(HSO3)3C3C1im][H2PO4], n-butyric acid with n-butanol 401
and [(HSO3)3C3C1im][OTf]
[(HSO3)3C3C1im][HSO4], [(HSO3)3C3C1im][BF4], [(HSO3)3C3C1im][PF6], and benzoic acid with ethanol 402
[(HSO3)3C3C1im][OTf]
[(HSO3)3C3C1im][HSO4] and [(HSO3)4C4C1im][HSO4] citric acid with n-butanol 403
[(HSO3)3C3Ph3P][OTs] acetic acid with ethanol 404
[(HSO3)3C3C1im][HSO4] and [(HSO3)pyr][HSO4] phthalic anhydride and sebacic acid with n-octanol and n- 405
butanol
[C1Pyrr][HSO4] gallic acid with n-propanol 406
1-[(1,1,1,2,3,3-hexafluoro-2-hydroxysulfonyl)propyloxyethyl]-3-methylimidazolium n-propanol with octanoic acid 407
chloride
[C6C1im][HSO4] and [C4C1im][H2PO4] neo-pentan-1-ol, hexan-1-ol, heptan-1-ol and decan-1-ol with 408
acetic acid, methoxyacetic acid and methylmalonic acid
BAIL with alkanesulfonic acid groups and a polyether oleic acid with methanol 409
[(HSO3)4C4C1im][HSO4] and [(HSO3)4C4(C2)3N][HSO4] salicylic acid with isoamyl alcohol 322
[(HSO3)3C3Ph3P][OTs] and acetic acid with ethanol 173
[(HSO3)3C3pyr][HSO4] benzoic acid with methanol, ethanol, and butanol 410
[C1Pyrr][HSO4] transesterification of dimethyl carbonate with phenol to 411
methylphenyl carbonate and diphenyl carbonate
[C4C1im][HSO4] oleic acid with methanol 412
[(HSO3)3C3(C2)3N][HSO4] and [(HSO3)3C3(C1)2H N][OTs] acetic, metacetonic and benzoic acid with ethanol, butanol, and 413,414
benzyl alcohol
[BzC1im][HSO4] stearic, palmitic and lauric acid with ethanol. 232
1-(4-butylsulfonic)-caprolactamium hydrogensulfate and [(HSO3)4C4C1im][HSO4] saponification of vegetable oil 415
[(HSO3)4C4C1im][OTs] palladium-catalyzed hydroesterification of olefins with 416
isosorbide
[(COOH)C1C1im][HSO4] arene carboxylic acids with alcohols 417

free radical alkylation reactions. Acid catalyzed alkylation is
generally an electrophilic alkylation. One common example is
the Friedel−Crafts type alkylation, in which a Lewis acid
catalyst is used to generate the carbocation, which acts as the
electrophile in the reaction. Lewis and Brönsted acidic ionic
liquids can be used to generate carbocations and the acidic
ionic liquids are often more effective than common Lewis and
mineral acids in these reactions. In 2013 Zhang et al. reviewed
the application of acidic ionic liquids as a catalyst in the
alkylation reaction.418 The methods used in the determination
of acidity, application of acidic ionic liquids in alkylation, acidic
adjustment methods, and novel acidic ionic liquids are
discussed in this review article with 38 references.418 Earlier
Qiao wrote a review on benzene alkylation with long chain
olefins catalyzed by ionic liquids as well, and this review is
particularly focused on the applications of chloroaluminate
ionic liquids in benzene alkylation of special interest to
petrochemical and detergent industry.419
6149
The Friedel−Crafts type alkylation at a carbon atom is the
most common application in acidic ionic liquid catalyzed
alkylations.420−424 However, there are examples of alkylations at
N, O and S atoms as well.425,426 Acidic ionic liquid catalyzed
alkylation of phenol and phenol derivatives like cresols are well-
known.427 Alkenes or tertiary alcohols such as t‑butanol are
common alkylating agents used in this reaction. For example,
Elavarasan and co-workers tested catalytic activities of three
BAILs in the t‑butylation of phenol with t‑butyl alcohol (TBA)
as shown in Figure 21.428 The reaction time, temperature, and
reactant/catalyst mole ratio were optimized in this study.
Among the three ionic liquids studied, triethylammonium based
sulfonic acid functionalized ionic liquid was found to be the
most promising and gave the highest phenol conversion. A
comparison of catalyst performances in the alkylation of phenol
with t‑butyl alcohol is shown in Table 11. Additionally they
found that the catalyst retained its activity even after 5 recycles.
The activation energy for ionic liquid catalyzed alkylation of
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Another widely studied application of acidic ionic liquids is

the alkylation of iso‑butane with 1-butene, and this is an
important process in the petroleum industry. The products are
often used as premium blending stock for reformulated gasoline
since they have a high octane number, low vapor pressure, and
low aromatic contents, alkenes and sulfur. Concentrated
Figure 21. t‑Butylation of phenol with t‑butyl alcohol (TBA) using sulfuric acid or hydrogen fluoride based methods are currently
different acidic ionic liquid catalysts: [(HSO3)4C4C1im][HSO4], being used in this process; however, these technologies are
[(HSO3)4C4pyr][ HSO4] and [(HSO3)4C4(C2)3N][ HSO4]428 gradually being restricted because of environmental pollution
and safety problems, creating a genuine quest for safer acid
Table 11. Comparison of Catalyst Performances in the catalysts. A number of research groups have studied
Alkylation of Phenol with t‑Butyl Alcohola chloroaluminate-based ionic liquids due to their standout
selectivity (%) acidity as catalysts in iso‑ butane 432−438 and isohexane
alkylation.439 In 1994, Chauvin et al.432 reported that the
conversion of 2- 4- 2,4- 2,6-
catalyst phenol (%) TBP TBP DTBP DTBP alkylation of iso‑butane with 2-butene could be efficiently
[(HSO3)4C4(C2)3N] 84.5 23.8 10.2 57.6 7.4
catalyzed by the ionic liquid 1-butyl-3-methylinidazolium
[HSO4] chloroaluminate. Since then, various chloroaluminate-based
[(HSO3)4C4pyr] 79.6 25.7 9.7 57.0 7.6 ionic liquids have been investigated as catalysts for iso‑butane−
[HSO4] butane alkylation by Yoo et al.,433 Xu et al.,434,435 Zhang et
[(HSO3)4C4C1im] 78.2 23.2 12.7 55.1 8.9 al.,436 Bui et al.,437 and so on. However, Lewis acidic
[HSO4]
a
chloroaluminate ionic liquids are extremely sensitive to
Reactant to catalyst ratio (phenol: IL) 1:1, reactant mole ratio (TBA: moisture and hydrolyze to release HCl in contact with traces
phenol) 2:1, temperature: 70 °C, reaction time: 8 h.428 of water. Brönsted acidic ionic liquids have also been utilized
for iso‑butane-butene alkylation.440,441 In one example, Cui and
phenol was found to be 11.13 kcal/mol in the 50−90 °C co-workers studied the alkylation of iso‑butane with 1-butene
temperature range.428 catalyzed by triflic acid (TFOH) coupled with a series of protic
In another type of an alkylation of a phenol involving a ammonium-based ionic liquids (AMILs), and they found that
multicomponent reaction, Hajipour et al. demonstrated that 2- addition of the AMILs can dramatically enhance the efficiency
naphthol can be alkylated with aldehydes and an amide or urea of TFOH for the alkylation reaction. 442 The alkylate
in the presence of a catalytic amount of Brönsted acidic ionic compositions produced by the optimized TFOH/IL with
liquid (4-butylsulfonic)-triethylammonium hydrogensulfate HSO4− anions are shown in Table 12. Under these conditions
[(HSO3)4C4(C2)3N][HSO4] under thermal, solvent-free con-
ditions in high yields, as shown in Figure 22.429 In addition,
Table 12. Alkylate Compositions Produced by the
Optimized TFOH/ILs with HSO4− Anions442a
C5−C7 C8 C9+ TMP/
ionic liquid (%) (%) (%) DMH RON
[HO2C2(C2)2HN] [HSO4] 3.8 88.9 7.3 12.1 97.4
(15 vol %)
[(HO2C2)2C1HN] [HSO4] 2.5 92.1 5.4 12.0 97.8
(15 vol %)
Figure 22. Brönsted acidic ionic liquid catalyzed one-pot synthesis of [(HO2C2)2C2HN] [HSO4] 3.5 87.3 9.1 13.5 97.4
1-amidoalkyl 2-naphthols429 (15 vol %)
[HOC1(C2)2HN] [HSO4] 3.8 89.6 6.6 12.9 97.7
(15 vol %)
Kotadia and Soni also used a silica supported −SO3H [[HO2C2C1H2N] [HSO4] 2.9 87.9 9.1 10.4 97.0
functionalized benzimidazolium based ionic liquid for the (15 vol %)
one-pot synthesis of a similar series of 1-amidoalkyl 2- [(C2)3HN] [HSO4] 1.9 91.5 6.6 13.5 98.0
(25 vol %)
naphthols.430
A series of acidic ionic liquids have been shown as excellent
a
Reaction conditions: temperature, 10 °C; pressure, 0.5 MPa; reaction
catalysts for the high-yielding synthesis of diphenolic acid time, 10 min; stirring speed, 1000 rpm.442
(DPA)431 as shown in Figure 23. Importantly, p,p′-DPA was
obtained as the preferential product over o,p′-DPA with an up to 85.1% trimethylpentanes (TMP) selectivity and 98
isomer ratio over 100. Moreover, diphenolic esters could also research octane number (RON) were achieved with the
be prepared in high yield through a one-pot method.431 optimized TFOH/AMIL catalyst (75 vol % triflic acid and 25

Figure 23. BAIL catalyzed synthesis of diphenolic acid (DPA). BAIL: [(HSO3)3C3C1im][CF3SO3], [(HSO3)3C3(C2)3N][CF3SO3], and
[(HSO3)3C3pyr][CF3SO3].

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Table 13. Selected Examples of Application of Acidic Ionic Liquids in Alkylation Reactions
acidic ionic liquid catalyst(s) reaction(s) refs
[C4C1im][HSO4], [C4C1im][HCO2] prolinium triflate (ProTf) indole + aldehydes/ketones → bis(indolyl)methanes 169,443,444
and [((HO)2C2)3N][HSO4]
[(C2)3NH][AlCl4] napthalene + iPrBr → 2-iPr napthalene 445
[(HSO3)4C4 C1im][OTf] phenol or anisole + alkene → alkylphenol or alkylanisole 446
[(HSO3)4C4(C2)3N][HSO4], [(HSO3)4C4Py][HSO4] and phenol + tBuOH → 2-TBP + 4-TBP + 2,4-DTBP + 2,6- 428
[(HSO3)4C4 C1im][HSO4] DTBP
[C4C1im][HSO4] hydroxybenzene + α,β-unsaturated compounds → oxa- 447
Michael adducts and Friedel−Crafts alkylated products
[C4C1im][AlCl4], [(C2)3NH][AlCl4], [[(C2)3NH][AlCl4−CuCl], i
butane/butene → octanes 448,449,193,435,450,451,440,433,442,452
[(C2)3NH][GaCl3] and [(C2)3NH][GaCl3−CuCl]
[(C2)3NH][AlCl4] toluene +2-chloro-2-methylpropane → p-tbutyltoluene 453,454
[(HSO3)4C4 C1im][OTf], [(HSO3)4C4 C1im][OTs] and glycerol + tBuOH → glycerol-tBu ethers 455
[(HSO3)4C4 C1im][HSO4]
[(HSO3)4C4 C1im][OTf] benzothiazole-2-thiole, aromatic amine, azole compounds, 425
indoles + benzylic alcohols → O, N, S, C benzylated
products
[(HSO3)3C3C1im][OTf], [(HSO3)3C3C1im][OMs], arene + aromatic aldehyde → triarylmethane 456
[(HSO3)3C3C1im][OTs], [(HSO3)3C3C1im][OTs] and
[(HSO3)3C3C1im][HSO4]
[(HSO3)3C3(C2)3N][HSO4], [(HSO3)3C3pyr][HSO4] and p-cresol + tbutanol →2-tBu-p-cresol and 2,6-ditBu-p-cresol 457−461
[(HSO3)4C4pyr][HSO4]
m-cresol + tbutanol → alkylated cresols
4
[(HSO3) C4 C1im][OTf] benzene +1-dodecene →2-phenyldodecane 462,463
silica immobilized phosphonium ionic liquid with In2Cl7− or InCl4− phenol + iButene →2-TBP, 4-TBP, 2,4-DTBP, 2,6-DTBP 464
[C4C1im][HSO4] isoprene + thiophene → desulfurization products 465
[(HSO3)4C4 C1im][HSO4] phenol + tbutanol →2-TBP, 4-TBP, 2,4-DTBP, 2,6-DTBP 466,467
[C4C1im][FeC14] benzene +1-octadecene octadecylbenzene 468
[(HSO3)4C4(C1)3N][HSO4], [(HSO3)4C4(C1)3N][OTs] and catechol + tbutanol →4-TBC + 3-TBC + TBCE 469,470
[(HSO3)4C4 Py][HSO4]
N-methyl-2-pyrrolidone hydrogensulfate phenol or thiol + alkene alkylated products. Coupling of 471,472
alcohols with styrenes
[(C2)3HN][AlCl4], [(C2)3HN][FeCl4], [(C2)3HN][ZnCl3], benzene + CH2Cl2 → diphenylmethane 473
[(C2)3HN][CuCl3] and [(C2)3HN][SnCl3], [(C2)3HN][SnCl5]
[(HSO3)4C4(C2)3N][HSO4] 2-naphthol+ aldehydes + amides or urea →1-amidoalkyl 2- 429
naphthols
[(C2)3HN][AlCl4] and [(C2)3HN][FeCl4] benzene +1-hexene → hexylbenzene 474
[C4 C1im][AlCl4] Ar−H + R-NCS → N-substituted thioamides 475
[(HSO3)4C4 C1im][HSO4] PhCOCH3 + ArCHO + CH3COCl + CH3CN → β- 264
acetamido ketones
[(HSO3)3C3C1im][OTf] and [(HSO3)3C3(C2)3N][OTf] levulinic acid + phenol → diphenolic acid 431
[C4 C1im][ZnCl3], [C4 C1im][FeCl4] and [C4 C1im][FeCl3] BzCl + Ar−H → diphenylmethanes 476
[(HSO3)3C3(C2)3N][ZnCl3] abietic acid → abietic acid dimer 477,478
4-(3-propylsulfonic)-4-butylthiomorpholinium 1,1-dioxide indoles + ketone →3-vinyl indoles 479
trifluoromethanesulfonate
1-(3-propylsulfonic)-3-alkylimidazolium-divinylbenzene copolymer Ar−H + BzOH → Ar- Bz 480
with PW12O403− anions
[C4C1im][AlCl4] diphenyl oxide +1-dodecene → monododecyl diphenyl 481
oxides
[(HO2C2)3HN][ CF3COO] knoevenagel reaction 482
[(HSO3)3C3C1im][HSO4] aldehydes +2-naphthol +2-aminobenzothiazole →1- 483
(Benzothiazolylamino) methyl −2-naphthols
[(HSO3)4C4Him][OTf], [(HSO3)3C3Him][HSO4] and aldol condensations 484,485
[(HSO3)3C3Him][H2PO4]
N-methyl-2-pyrrolidone hydrogensulfate 1,8-dioxo-octahydroxanthene derivatives 486
[(HSO3)4C4C1im][OTf] 1,3-dioxanes via Prins reaction 487
[(HSO3)2C2(SO3)H2N][HSO4], [(HSO3)2C2(SO3)H2N][OTf], nitrostyrene from Henry reaction. α-amino-phosphonates 488,489
[(HSO3)2C2(SO3)H2N][NO3] and [(HSO3)2C2(SO3)H2N]
[Tfa]
[(HSO3)4C4(C2)3N][OTs] condensation of n-butyraldehyde to 2-ethyl-2-hexenal 490
1-ethyl-1,2,4-triazolium methanesulfonate β-amino carbonyl compounds 491
[C1Him][H2PO4] alkyl aza-arene addition to aldehydes 492

vol % triethylammonium hydrogen sulfate), which were much
better than those obtained with the commercial H2SO4 catalyst
(65% TMP selectivity, 97 RON) and pure triflic acid.442
6151
As described earlier there are numerous applications of acidic
ionic liquids in alkylation reactions and some selected examples
and their references are shown in Table 13.
9.1.3. Acetalization. Acetalization is another acid catalyzed
reaction tested with BAILs, where (4-butylsulfonic)-triethy-
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Chemical Reviews
lammonium hydrogensulfate [(HSO3)4C4(C2)3N][HSO4] was
reported to give excellent yields in the production of fructone
via the acetalization reaction of ethyl acetoacetate with ethylene
glycol.325,493 The condensation of glycerol, a platform chemical
from renewable materials with benzaldehyde to generate cyclic
acetals has been investigated using BAIL catalysts. Evidence was
presented for the formation of a product mixture with 4-
hydroxymethyl-2-phenyl-1,3-dioxolane and 5-hydroxyl-2-phe-
nyl-1,3-dioxane as cis and trans stereoisomers. Under optimum
reaction conditions butyl-pyridinium hydrogensulfate [C4pyr]-
[HSO4] catalyst produced a 99.8% yield of acetals at room
temperature.494
9.1.4. Heterocyclic Synthesis. The use of Brönsted acidic
ionic liquids in heterocyclic synthesis is a well documented
application. A fair number of classical heterocyclic syntheses
done with Lewis and Brönsted acids have been tested with
BAILs and in many cases BAILs have proven to be better
catalysts than equivalent dose of traditional acids. Some of the
initial applications are discussed in a few earlier ionic liquid
review articles495−498 and in a book titled “Ionic Liquids in
Synthesis”.499 The 2008 review titled “Ionic Liquids in
Heterocyclic Synthesis” with 367 references gives a compre-
hensive account on the use of neutral, acidic and basic ILs as
solvents and catalysts in the synthesis of many classes of
heterocyclic compounds.500
In a recent application, 1-(3-propylsulfonic)-3-methylimida-
zolium chloride [(HSO3)3C3C1im][Cl] and 1-(4-butylsul-
fonic)-3-methylimidazolium chloride [(HSO3)4C4C1im][Cl]
BAILs are shown as excellent catalysts and reaction mediums
for Skraup synthesis of quinolines under microwave con-
ditions501 (Figure 24). There are a number of advantages to
Figure 24. 1-(Alkylsulfonic)-3-methylimidazolium chloride Brönsted
acidic ionic liquid catalyzed Skraup synthesis of quinolines under
microwave heating.
using the BAILs as reaction mediums and catalysts in the
Skraup synthesis. These include: shorter reaction time, better
yields, ease of isolation of the quinoline product, and most
importantly elimination of the use nitrobenzene or other
oxidizing agents and additional metal catalysts.501
The BAILs on solid supports have been used in heterocyclic
synthesis.502 In this application, Fe2O3-MCM-41 materials with
1-(4-butylsulfonic)-3-propylimidazolium hydrogensulfate has
been used as the catalyst for the one-pot synthesis of
pyrimido[4,5-d]pyrimidine derivatives as well as 2-amino-4H-
chromenes503 using 6-aminouracil, aldehydes, and urea or
thiourea under solvent free conditions.504 Some selected
examples of heterocyclic synthesis using acidic ionic liquids as
catalysts are shown in Table 14.
9.1.5. Carbonium Ion Generation and Rearrange-
ments. Acidic ionic liquid catalyzed carbonium ion generation
and rearrangements of the resulting carbonium ions is another
reaction receiving attention. In many examples the carbonium
ion rearrangement product distributions are influenced by the
AIL catalysts as compared with traditional acids. The use of
6152
Review
Brönsted acidic ionic liquids to generate the carbonium ions
and subsequent reactions in the ionic liquid media is known in
named reactions like the pinacol rearrangement173 and Ritter
reaction558 as well as in isomerizations.559 Kalkhambkar558 and
co-workers have used imidazolium ionic liquid 1-(4-butylsul-
fonic)-3-methylimidazolium triflate [(HSO3)4C4 C1im][OTf]
as catalyst for the high yield synthesis of a wide variety of
amides under mild conditions via the Ritter reaction of alcohols
with nitriles as shown in Figure 25.
In another recent work efficient and selective rearrangements
of stilbene epoxides were observed with 0.1−0.3 equiv of
[(HSO3)4C4C1im][OTf] in dichloromethane as shown in
Figure 26. A substituent effect study was performed with a
series of singly substituted 1,2-diphenyl oxiranes and competing
formation of ketones was observed in acidic ionic liquids.560
In another application propargylic alcohols were converted to
cyclic and acyclic α,β-unsaturated enones using
[(HSO3)4C4C1im][OTf] as the catalyst and [C4C1im][PF6]
as the solvent via the Rupe rearrangement as shown in the
example in Figure 27.561
Pinacol rearrangement of hydrobenzoin using triethylammo-
nium hydrogensulfate [(C2)3NH][HSO4] as the catalyst is
another example for carbonium ion generation and rearrange-
ment as shown in Figure 28.562 The optimal conditions were
found to be heating at 80 °C for 5 min under low power
microwave (20 W) conditions to avoid ionic liquid degradation.
Lewis acidic ionic liquids like pyridinium chloroaluminate has
been used in isomerization of exo-tetrahydrodicyclopentadiene
to adamantane.563,564 Rearrangements of terpenes is another
area of interest, where 1-(3-propylsulfonic)-3-methylimidazo-
lium dihydrogen phosphate [(HSO3)3C3C1im][H2PO4] has
been used as the catalyst in the synthesis of α-terpineol from α-
pinene.565 The same group reported 1-(1-ethyl acetate-yl)-3-
methylimidazolium chloroaluminate catalyzed isomerization of
α-pinene to camphene as well.566
9.1.6. Dehydration. The acid catalyzed dehydration of an
alcohol to yield an alkene is another well established synthetic
operation and has been known with acidic ionic liquid catalysts
as well. Dehydration of glycerol to acrolein is a new renewable
resources based route to this C3 aldehyde; liquid phase170 as
well as solid supported acidic ionic liquid catalyzed methods are
reported to this important feedstock in the recent liter-
ature.567,568 Shen and co-workers have investigated a liquid
phase dehydration of glycerol to acrolein catalyzed by BAIL
using the semibatch reaction technique. They found that for a
series of BAIL catalysts, the acrolein yields were in the order of
[C4C1im][H2PO4] > [C4C1im][HSO4] > [C4Py][HSO4] >
[(HSO3)3C3Py][HSO4] > [C4(C2)3N][HSO4] >
[(HSO3)3C3Py][H2PO4] > [C4Py][H2PO4] > [C4(C2)3N]-
[H2PO4]. When [C4C1im][H2PO4] and [C4C1im][HSO4]
were used as the catalysts at 270 °C with the molar ratio of
catalyst to glycerol of 1:100, the acrolein yields were 57.4% and
50.8%, respectively, at complete conversion of glycerol.170
Nevertheless in the dehydration of ethanol to ethylene, Gong et
al. found that the catalytic activity of 1-(4-butylsulfonic)-3-
methylimidazolium hydrogen sulfate [(HSO 3) 4C4 C1 im]-
[HSO4] is similar to H2SO4.569
9.1.7. Oxidation. In another application BAIL catalysts
have been used in the oxidation of alcohols to aldehydes and
ketones. In this instance, −SO3H functionalized heteropolyan-
ion-based ionic liquids with 35% aqueous H2O2 were used
without adding any phase transfer catalyst as shown in Figure
29.570 For the aliphatic alcohols corresponding aldehydes and
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Table 14. Applications of Acidic Ionic Liquids in Heterocyclic Synthesis

acidic ionic liquid catalyst(s) reaction refs
[C4C1im][HSO4] hydrazines +1,3-dicarbonyls → pyrazoles. 4-hydroxyquinoline-2-one 505,506
+ Meldrum’s acid + aldehyde → pyrano[3,2-c]quinoline-2,5-diones
[C1Him][Tfa] and Cu(OAc)2/sodium ascorbate propargylated aldehydes + azides +2-aminobenzophenone + 507
ammonium acetate → phenylquinazolines
choline chloride · 2ZnCl2 quinolines via Friedländer annulation 508
[C4C1im][HSO4] and [(HOOC)C1 C1im][HSO4] aldehydes + methyl acetoacetate + urea or thiourea →3,4- 509,510
dihydropyrimidin-2(1H)-one and 3,4-dihydropyrimidine-2(1H)-
thione (Biginelli reaction)
[C1Him][Tfa] dimedone + aldehyde →1,8-dioxooctahydroxanthenes 511
dimedone + aldehyde + R-NH2 → 1,8-dioxodecahydroacridine
[C4C1im][ZnCl3] o-amino aromatic carbonyls + ketones → quinolines (Friedländer 512
synthesis)
[C4C1im][HSO4] and [C4C1im][OTf] phenol + methyl acetoacetate → coumarins 167,513
polymer supported [(HSO3)3C3pyr][1/3. PW12O40] anthranilamide + aldehydes →2,3-dihydro-4(1H)-quinazolinones 216
[(HSO3)4C4 C1im][HSO4], [(HSO3)4C4 C1im][OTs], [(HSO3)4C4 C1im] pyrrole + cyclohexanone → N-confused meso-tetraspirocyclohexyl 514,515
[OMs] and N-methyl-2-pyrrolidonium tosylate calix[4]pyrrole
[(HSO3)4C4(C2)3N][HSO4] Ar−CHO + cyclopentanone + urea/thiourea → pyrimidinone 516
3-carboxypyridinium hydrogensulfate 1,3-dicarbonyl + Ar−CHO and urea/thiourea →3,4- 517
dihydropyrimidin-2(1H)- ones
[C1Him][HSO4] ethylacetoacetate + R-CHO + urea/thiourea →3,4-dihydropyrimidin- 518,519
2(1H)-ones and thiones and piperidines
[(HSO3)3C3C1im][HSO4] and [(HSO3)3C3C1im][OTf] ketones + pyrrole → calix[4]pyrroles and N-confused calix[4] 520−524
pyrroles, 21-thia-5,10,15,20-tetraarylporphyrins, 2-aryl-1-arylmethyl-
1H-benzimidazoles
[(HOOC)C1 C1im][OTf] ArCHO + dimedone + NH4OAc → Acridinedione 525
[(HSO3)3C3(C2)3N][HSO4] ArCHO + dimedone →1,8-dioxo-octahydroxanthenes 526
[C4C1im][HSO4], [C4C1im][H2PO4] and [C6C1im][BF4] resorcinol + methyl acetoacetate →7-hydroxy-4-methylcoumarin 317
caprolactam tetrafluoroborate cyclohexanone oxime → caprolactam 527
[(HSO3)3C3(C2)3N][HSO4] α-oxothioformanilide + o-phenyldiamine → quinoxaline 528
[(HSO3)3C3C1im][Cl], [(HSO3)3C3C1im][H2PO4], [(HSO3)3C3C1im] Ph-NHNH2 + cyclohexanone → indoles 318
[HSO4], [(HSO3)4C4C1im][Cl], [(HSO3)4C4C1im][H2PO4], and
[(HSO3)4C4C1im][HSO4]
1,1′-butylenebis(3-methylimidazolium) hydrogen sulfate 2-amino-3-pyridinecarbonitrile → tacrine analogue and 13-(aryl)- 529,530
12H-benzo[f]indeno[1,2-b]quinoline-12-one
[(HSO3)4C4pyr][HSO4] 2-aminobenzamide + ArCHO → 2-aryl-2,3-dihydroquinazolin-4 263
(1H)-ones
1,4-dimethyl-1,4-bis(4-butylsulfonic)piperazinium hydrogensulfate pyranopyrazoles, benzopyrans, amino-2-chromenes and 531
dihydropyrano[c]chromenes
[(C2)3HN][ZnCl3] condensation of isophytol and trimethylhydroquinone in the 532
synthesis of vitamin E
[(HSO3)4C4pyr][AlCl4] polymer supported biscoumarins by domino Knoevenagel-Michael addition 533,289,298
[(HSO3)C4im][Cl] hexahydroquinolines 534
[(HSO3)4C4pyr][HSO4] polymer supported 1-amidoalkyl-2-naphthols and substituted quinolines 218
hexamethyltetrammonium sulfonic acid-phenol-formaldehyde resin Peckmann reaction 535
[C1C3im][HSO4] immobilized on nanoporous Na+-montmorillonite 4,4-(arylmethylene)-bis(3-methyl-1-phenyl-1H-pyrazol-5-ol) 279
N-methyl-2-pyrrolidonium hydrogensulfate pyrano[2,3-c]pyrazoles 197
[(HSO3)3C3Ph3P][OTs] N-methyl-2-pyrrolidonium hydrogensulfate 14-aryl-14H-dibenzo[a,i]xanthene-8,13-dione, 3,4-dihydro-2H-benzo 536,537
[b]xanthene-1,6,11(12H)-trione
[(HSO3)4C4C1im][HSO4] spiro[diindenopyridine-indoline]-triones by condensation of 1,3- 538,539
indandione, isatin and aniline.
benzothiazoloquinazolines by reaction of 2-aminobenzothiazoles, α-
tetralone, and furan-2-carboxaldehyde
N-methyl-2-pyrrolidonium hydrogensulfate furan-2(5H)-ones. 540−544
2,3-dihydroquinazolin-4(1H)-ones
[(HSO3)4C4C1im][OTf] 1,3-dioxanes via the Prins reaction 487,545
[C1Him][HSO4] Knoevenagel-hetero-Diels−Alder reaction. 546
[(HSO3)4C4C1im][OBs] pyrano[3,2-c]quinolin-2-one derivatives by the tandem cyclization of 547
4-hydroxy-1-methyl-2-quinolone with chalcones
N-methyl-2-pyrrolidonium dihydrogen phosphate 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthene-11-ones. Spiro 548,549
[diindenopyridine-indoline]triones
[(HSO3)4C4C1im][HSO4] pyrido[2,3-d]pyrimidines 550
[C6C1im][HSO4] N-substituted pyrroles by Clauson Kaas reaction 551
[(C2)2H2N][ClSO3] and [(C4)2H2N][ClSO3] 2-mercaptonaphthalen-1-yl-methyl-3-hydroxy-5,5-dimethylcyclohex- 552,553
2-enones
[(Py)2SO][HSO4]2 ketone + thiosemicarbazide → spiro-1,2,4-triazolidine-3-thiones 554
[(C2)3HN][HSO4] azlactones/oxazolones 555
[(HSO3)2im][HSO4] pyrimido[4,5-b]quinolines 556

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Table 14. continued
acidic ionic liquid catalyst(s)
3-sulfonic-1-imidazolopyridinium hydrogensulfate
[(HSO3)4C4(2-HSO3−Ph)3P][HSO4]
Figure 25. [(HSO3)4C4C1im][OTf] catalyzed Ritter reaction558
Figure 26. [(HSO3)4C4 C1im][OTf] catalyzed rearrangements of
stilbene epoxides560
Figure 27. [(HSO3)4C4C1im][OTf] catalyzed rearrangement of a
propargylic alcohol to α,β−unsaturated enone via the Rupe rearrange-
ment.561
Figure 28. Pinacol rearrangement of hydrobenzoin under microwave
irradiation using [(C2)3NH][HSO4] catalyst562
Figure 29. Oxidation of alcohols with H2O2 catalyzed by long chain
−SO3H functionalized heteropolyanion-based ionic liquids under
solvent-free conditions.570
ketones were obtained in 63%−100% yields using SiW12O404−
anions. For benzyl alcohols, the corresponding benzoic acids
were obtained in 64%−94% yields using PW12O403− anions.
Table 15. Application of Acidic Ionic Liquids in Polymerization and Oligomerization Reactions
acidic ionic liquid catalyst(s)
[C4C1im][AlCl4] and [(EtOCOCH2)C1im][AlCl4]
[(HSO3)4C4 C1im][OTf], [(HSO3)4C4 C1im][BF4], [(HSO3)4C4 C1im][OTs], [(HSO3)4C4 C1im][HSO4],
[(HSO3)4C4 Py][ HSO4] and
[(HSO3)4C4 (alkyl)im][HSO4] supported on silica gel
[HPyrr][HSO4]
Multi-SO3H-functionalized ionic liquid
Review
reaction refs
2H-indazolo[2,1-b]phthalazine-1,6,11(13H)-triones 180
pyrano pyrimidinones 557
After the completion, two ionic liquids could be reused five
times after simple removal and without significant loss of their
catalytic activities.
In another oxidation by silver tungstate nanorods in a
Brönsted acidic ionic liquid (1,2-dimethyl-3-dodecylidazolium
hydrogensulfate) cyclohexene has been converted to adipic acid
using 30% H2O2 as the oxidant.571
9.1.8. Polymerization and Related Reactions. Acidic
ionic liquids can be used as catalysts for polymerization as well
as synthetic modifications of polymers like cross-linking and
functionalizations.572 Methylimidazolium hydrogensulfate has
been used as the catalyst for polymerization of L-aspartic acid to
polyaspartic acid under microwave irradiation.573 Tian et al.
demonstrated that 1-vinyl, 3-(3-propylsulfonic) imidazolium
hydrogensulfate works as a “quasi-homogeneous” catalyst for
the acetylation of cellulose.574 Unlike existing techniques that
use a large amount of ILs as solvent to dissolve and acetylate
cellulose, a small amount of acidic IL was used as the catalyst in
this study to overcome the low efficiency associated with
relatively high viscosity and costs of ILs during homogeneous
acetylation. Fully substituted cellulose acetate with a conversion
of 88.8% was obtained by using only 9 mol % of the catalyst,
which is still higher than common commercialized solid acid
catalysts.574 Some other applications include BAIL catalyzed
synthesis of 2-dimethylaminoethyl methacrylate-dicarboxylate
polymer adhesives,575 1-(3-propylsulfonic)-3-methylimidazo-
lium hydrogen sulfate [(HSO3)3C3C1im][HSO4] catalyzed
methanolysis of poly(lactic acid),576 glycolysis of PET,577,578
depolymerization of PET using 1-hexyl-3-methylimidazolium
hydrogen sulfate [C6C1im][HSO4],579 and degradation of
chitosan.580 Selected applications of the use of acidic ionic
liquid catalysis to prepare polymers and oligomers are outlined
in Table 15.
9.1.9. Miscellaneous Catalysis Applications. The
preparation of glycerol dimethyl ether (2,3-dimethoxy-1-
propanol), a potential fuel additive, from glycerol using AIL
catalysts is a noteworthy application.586 This route uses both
glycerol and methanol as starting materials, by way of
epichlorohydrin as an intermediate product, and utilizes HCl
as a recycling agent. Among various BAIL catalysts investigated,
the acidic ionic liquid (4-butylsulfonic)-trimethylammonium
hydrogensulfate [(HSO3)4C4(C1)3N][HSO4] exhibited the
highest activity and selectivity in the process.586 N-Boc
protection of amines is a common synthetic operation. Shirini
and co-workers have introduced a new class of BAIL,
polymerization/oligomerization reaction refs
α-pinene polymerization 581,582
copolymerization of lactic acid and ε- 583
caprolactone
oligomerization of isobutene 265
homo and graft polymerization of ε- 584
caprolactone
polymerization of lactic acid-ethylene 585
glycol
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succinimidinium hydrogensulfate, as efficient catalysts for the
room temperature amine protection reaction under neat
conditions.587 The miscellaneous catalysis applications of
BAILs include: the insertion of α-diazoacetate into the N−H
bonds of amines,485 regioselective thiocyanation of aromatic
and heteroaromatic compounds at room temperature,588 and
conversion of alcohols to azides.589
Selective nitration of phenols is another instance where
nitration with sodium nitrate could be carried out in the
presence of acidic ionic liquid 1-butyl-3-methylimidazolium
hydrogen sulfate [C4C1im][HSO4] at room temperature, in
good to high yields and short reaction times.590 Furthermore,
regioselective mononitration of chlorobenzene has been
investigated in the HNO3−Ac2O system with caprolactam
based BAILs as shown in Figure 30.591 The sequence of
Figure 30. Caprolactam based BAIL catalyzed regioselective
mononitration of chlorobenzene591
nitrification activity is [CP][HSO4] > [CP][p-TSA] > [CP]-
[BSA]. The mole ratio of chlorobenzene to ionic liquid was
10:1.5, at 60 °C and the reaction time was 2.5 h, the yield of
mononitro-chlorobenzene could reach 71.22%; and the mass
ratio of para/ortho isomer was 7.74, which was much more
than 2.0 of para/ortho isomer mass ratio obtained by nitric-
sulfuric mixed acids as catalyst. Besides, the ionic liquid could
be used repeatedly.591 Acidic ionic liquid catalyzed direct
nitration of 1,4,5,8-tetraaza-bicyclo-[4,4,0]-decane to synthesize
1,4,5,8-tetranitro-1,4,5, 8-tetraazabicyclo-[4,4,0]-decane
(TNAD) with N2O5 is also another interesting application.592
9.2. Carbon Dioxide Dissolution and Fixation
Dissolution and fixation of CO2 is an important green
chemistry topic of current interest, which include the reduction
and utilization of captured CO2 for the synthesis of valuable
chemicals.593 Amide-based Brönsted acidic ionic liquids are
well-known for their good CO2 absorption characteristics.594,595
Deng et al. has prepared a series of amide-based Brönsted acidic
ionic liquids by acid−base neutralization reaction of N,N-
dimethylformamide (DMF), N,N-dimethylacetamide (DMAc),
and N-methylpyrrolidone (NMP) with trifluoroacetic acid
(TFA) or tetrafluoroboric acid (FBA). The solubility data of
CO2 in these BAILs was determined at different temperatures
and sub atmospheric pressure using isochoric saturation
method. In these experiments they found that, with the same
cation CO2 solubility in TFA-based BAILs are higher than that
in FBA-based ones.594 Mumford et al. recently evaluated the
protic ionic liquid ethylenediamine N,N-dimethylaminoethy-
lammonium formate for the removal of CO2 from N2 mixed gas
streams.596 This evaluation was conducted by comparison with
the industrial standard 30 wt % monoethanolamine (MEA).
These studies demonstrated that the sorption process included
a chemical reaction component and is comparable to MEA;
however, the mass transfer coefficient is an order of magnitude
lower than MEA, which was likely due to the higher viscosity of
the ionic liquid and its impact on carbon dioxide diffusivity.596
6155
Review
9.2.1. Cyclic Carbonate Synthesis. Cyclic carbonates are
valuable industrial raw materials and acidic ionic liquids are
excellent catalysts for the preparation of cyclic carbonates from
epoxides and carbon dioxide.143,597 A variety of acidic ionic
liquids have been shown to be good catalysts for this process,
which includes; imidazolium, pyridinium, triethanolammonium
protic and −SO 3 H functionalized ionic liquids, 143,598
[(HO2C)2C2Ph3P][Br],599 2-(N,N-
dimethyldodecylammonium)acetic acid bromide,319 and car-
boxyl-isobutyl-functionalized immobilized ionic liquids.284 Xiao
and co-workers studied a series of protic ionic liquids for the
synthesis of propylene carbonate from CO2 and propylene
oxide as shown in Figure 31.143 The effect of protic acid ionic
liquid catalysts on the synthesis of propylene carbonate is
shown in Table 16.
Figure 31. Protic acid ionic liquid catalyzed synthesis of propylene
carbonate from propylene oxide and carbon dioxide.143
Table 16. Effect of Protic Acid Ionic Liquid Catalysts on the
Synthesis of Propylene Carbonatea143
entry protic ionic liquid catalyst yieldc (%)
1 methylimidazole (C1im) trace
2 methylimidazolium bromide [C1Him][Br] 94.5
3 imidazoliumiodide [Him][I] 93.3
4 triethylammonium bromide [(C2)3HN][Br] 34.9
5 pyridinium bromide [HPy][Br] 31.6
6 methylimidazolium chloride [C1Him][Br] 47.4
7 methylimidazoliumiodide [C1Him][I] 91.8
8 ethylimidazolium bromide [C2Him][Br] 85.8
9 butylimidazolium bromide [C4Him][Br] 77.7
10b methylimidazolium bromide [C1Him][Br] 59.8
a
Reaction conditions: propylene oxide 5.0 mL, catalyst 1.0 mol %,
CO2 1.5 MPa, 120 °C, 2.0 h. bCatalyst 0.5 mol %. cIsolated yield and
the selectivity >99%.
In another example Gao and co-workers proved that a
polystyrene-supported Lewis acidic iron-containing ionic liquid
is a recyclable heterogeneous catalyst for converting CO2 into
cyclic carbonates.130 Notably, the catalyst could be readily
recovered and reused over five times without appreciable loss of
catalytic activity. Additionally the protocol has been applied to
reactions of aziridines/propargyl amines with CO2.130 Carboxyl
functionalized dication imidazolium-based ionic liquids have
also been evaluated as efficient catalysts for the synthesis of
cyclic carbonates from epoxides and CO2 in the absence of a
cocatalyst and a solvent.600
9.2.2. Urea Synthesis. Lewis acidic ionic liquids are known
to catalyze the reaction of CO2 with amines to give ureas. Yao
et al. reported the use of [C4C1im][AlCl4] as the catalyst and
solvent, for the reaction of CO2 with aniline at 160 °C,
producing 1,3-diphenyl urea in 17.9% yield and 98.9%
selectivity as shown in Figure 32.601
9.3. Ionogels, Electrolyte, Battery, and Capacitor
Applications
Mizumo and co-workers reported a thermally stable, water-free
proton conductor based on Brönsted acidic ionic liquid and
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Chemical Reviews
Figure 32. Lewis acidic ionic liquid catalyzed synthesis of 1,3-diphenyl
urea.
silicate network.602 This material was prepared with a mixture
of bis(trifluoromethyl sulfonyl)imide and 1-(4-butylsulfonic)-3-
methylimidazolium hydrogen sulfate by using the sol−gel
process. The ionic conductivity of the ionogel reached 10−3 S
cm−1 at 150 °C without any humidification.602
Acidic ionic liquids have been studied as electrolytes for
several applications like battery electrolytes, electrophoresis
media and electroplating media.603 Rezaei et al. studied the
electrochemical and corrosion behaviors of alkyl ammonium
hydrogensulfates as electrolyte additives on Pb alloy electrodes
of the lead-acid battery.604 A few acidic ionic liquids such as
[(C6H5CH2)(C1)2HN][AlCl4] have been tested as electrolytes
for batteries.605,606 Then there is an example in the use as a
solar cell electrolyte, where the acidic ionic liquid polymer
poly[((3-(4-vinylpyridine) propanesulfonic acid) iodide)-co-
(acrylonitrile)] works as an ionic liquid electrolyte for dye-
sensitized solar cells.607 The cell based on electrolyte containing
20 wt % poly-AIL yielded an overall energy conversion
efficiency of 6.95% under AM 1.5 illumination at 100 mW
cm−2.607 A number of acidic ionic liquids have been used as
neat liquids as well as additives in electrodeposition experi-
ments, which include: [C4C1im][HSO4],608,609 [C2py][HSO4],
[C4py][HSO4] and [C6py][HSO4] in the electrodeposition of
zinc,610 [(C2)4N][HSO4], [(C4)4N][HSO4],611 [C4py][HSO4]
and [C 6 py][HSO 4 ] in copper electrodeposition, 612,613
[(C1)3HN][Cl],614 [(C2)3HN][Cl]615 in the electrodeposition
of Al, [C2C1im][AlCl4] in the electrodeposition of Al−W
alloy616−618 and octyl-3-methylimidazolium chlorogalate in the
electrodeposition of Ga.619
9.4. Fuel-Cell Applications
The use of acidic ionic liquids as electrolytes in fuel-cells is an
emerging field due to their high conductivity, as well as their
thermal, chemical and electrochemical stability.620,621,338,622
Yasuda et al. investigated diethylmethylammonium trifluor-
omethanesulfonate [(C2)2C1HN][OTfs], which exhibits favor-
able bulk properties and electrochemical activity for fuel-cell
applications. In this case solid thin films containing
[(C2)2C1HN][OTfs] were fabricated using sulfonated poly-
imide as a matrix polymer and used in nonhumidifying fuel cell
operation at 120 °C.621,623
Many research groups have studied the use of protic ionic
liquids as a component in composite proton exchange
membranes (PEMs) for the next generation fuel cells.624−626
The protic ionic liquids studied in this application include 1-
vinylimidazolium trifluoromethanesulfonate [(CH2CH)-
Him][OTf],627 1-methyl-imidazolium trifluoromethanesulfo-
nate [C1Him][OTf],628 and polymer electrolyte membranes
based on poly(ethylene oxide)/1-butyl-3-methylimidazolium
hydrogen sulfate [4C4C1im][HSO4].629 In another approach
the acid retention capability of poly(4,4′-diphenylether-5,5′-
bibenzimidazole) (OPBI) nanocomposite membranes in fuel
cells could be enhanced by incorporating protic ionic liquids.625
In this case silica nanoparticles of 25 nm size were prepared,
successfully modified with phosphate anion containing
imidazolium AILs and were incorporated in OPBI by solution
blending method.625
6156
Review
Protic ionic liquid based membranes have been tested in
polymer electrolyte membrane fuel cells. In this instance Nafion
membranes impregnated with the protic ionic liquids 1-(4-
butylsulfonic)-3-methylimidazolium bis(trifluoromethyl-
sulfonyl)imide [(HSO3)4C4C1im][NTf2], 1-(4-butylsulfonic)-
3-methylimidazolium bis trifluoromethanesulfonate
[(HSO3)4C4 C1im][OTf] and membranes based on the
polymerization of 1-(4-butylsulfonic)-3-vinylimidazolium tri-
fluoromethanesulfonate [(HSO3)4C4(CC)im][OTf] were
tested. This is the first report that describes the application
of a polymerized protic ionic liquid membranes for fuel cells.630
An alternative approach is the immersing of the membranes
based on imidazolium ionic liquids with 1-butyl-3-methylimi-
dazolium dihydrogen phosphate [C4C1im][H2PO4] and
polymers of sulfonated poly(ether−ether) ketone (SPEEK)
or polyvinylidenefluoride (PVDF) into pure phosphoric acid at
room temperature. A composite membrane fabricated by this
method has achieved proton conductivity of 3.0 × 10−2 S cm−1
at 160 °C under anhydrous conditions.631
9.5. Electrophoresis Applications
In an interesting chromatography application N-methyl-2-
pyrrolidonium methyl sulfonate acidic ionic liquid has been
used as a new dynamic coating for separation of basic proteins
by capillary electrophoresis.632 The authors found that AIL
modified capillary not only generated a stable suppressed
electro osmotic flow, but also effectively eliminated the wall
adsorption of proteins.
9.6. Membrane Applications
Acidic ionic liquid incorporated membranes are known and
these materials are particularly useful for the separation of
gases633,634 as well as incorporation of ion exchange and
antibiofouling properties.635 Huang et al. reported the
preparation and use of dicarboxylate-based IL incorporated
membranes as a class of tunable media for the selective
separation of acidic gases.633 When the anions of dicarboxylate-
based ILs are fully deprotonated, they could be used as effective
carriers for the selective separation of CO2. The permeabilities
of CO2 in triethylbutylammonium malonate
[C4(C2)3N]2[malonate] and triethylbutylammonium maleate
[C4(C2)3N]2[maleate] under the partial pressure of 0.1 bar
range from 2147 to 2840 barrers and the permselectivities of
CO2/N2 and CO2/CH4 in them approach to 178−265 and
98−221, respectively. However, when the anions of dicarbox-
ylate-based ILs are half deprotonated, they are efficient solvents
for the selective separation of SO2.633 The application of
encapsulated ionic liquids within porous moieties in the proton
exchange membranes field is described in a book chapter by
Eguizábal and Pina as well.636
Nafion-polymeric acidic ionic liquid composite membranes
with different cations have been studied for their physical
properties.637 In general, the Nafion/polymeric IL composite
membranes exhibit a significant increase in the ionic
conductivities than Nafion under anhydrous conditions. The
interactions between the Nafion ionomer and different
geometric cations of polymeric ILs were also discussed by Lu
et al. in the comparison of nanostructures, dynamic-mechanical
properties, and thermal stabilities of the Nafion/polymeric IL
composite membranes.637 The molecular dynamics and ion
transport studies on polymerized imidazolium-based protic
ionic liquid [(HSO3)4C4(CC)im][OTf] have indicated a
strong decoupling between conductivity relaxation times σσ
(related to the ions migration through the polymer matrix) and
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segmental dynamics when the ionic transport is controlled by
fast proton hopping through the dense hydrogen-bond
network.638 Some selected examples of the use of acidic ionic
liquids in ion conducting membranes are shown in Table 17.
Table 17. Use of acidic ionic liquids ion conducting
membranes
AIL membrane application refs
diethylmethylammonium triflate [(C2)2C1HN][OTf] doped 639
Nafion membrane
triethylammmonium triflate [(C2)3HN][OTf] doped Nafion- 640,641,639
membranes
diethylmethylammonium triflate [(C2)2C1HN][OTf] proton 621
conductivity
alkylammonium hydrogensulfate [RH3N][HSO4] in 642,643
permeation of chromium(III) using ionic liquid and
pseudoemulsion hollow fiber strip dispersion.
N,N-dimethylpyrrolidinium methylphosphite membrane 644
[(C1)2Pyrr][MeHPO3] for the separation of acetylene/
olefin mixtures
9.7. Conversion of Biomass to Renewable Feedstock
Chemicals
9.7.1. Renewable Furans, Levulinic Acid, and Related
Compounds. Acidic ionic catalyzed dehydration of carbohy-
drates to 5-hydroxymethylfurfural, furfural, and levulinic acid
and related compounds has emerged as an active research area
in the last 4−5 years due to the current interest in renewable
feedstocks and fuels. Dehydration of carbohydrates to furan
derivatives is the most widely studied reaction, and the
common dehydration of fructose to 5-hydroxymethylfurfural
(HMF) occurs via elimination of three molecules of water as
shown in Figure 33. 645,646 Acidic ionic liquids 1-(4-
butylsulfonic)-3-methylimidazolium hydrogen sulfate,647,648,350
1-(4-butylsulfonic)-3-allylimidazolium hydrogen sulfate trifluor-
omethanesulfonate,649 N-methyl-2-pyrrolidonium hydrogen
sulfate,329 1-methyl-3-(butyl-4-chlorosulfonyl) imidazolium
chlorosulfate,650 1-ethyl-3-methylimidazolium hydrogen sul-
fate,651 dimethylimidazolium hydrogensulfate,652,653 dimethyl-
benzaimidazolium hydrogensulfate,652 1-carboxymethyl-3-
methyl imidazolium chloride,654 1-carboxypropyl-3-methyl
imidazolium chloride,655 and Cr3+ containing SO3H-function-
alized polymeric BAILs656 have been reported as catalysts.
Acidic ionic catalyzed dehydration of D-glucose to 5-
hydroxymethylfurfural is also known.657 Amarasekara and
Razzaq have proposed a mechanism for 1-(1-propylsulfonic)-
3-methylimidazolium chloride catalyzed transformation of D-
glucose to HMF using NMR studies of C-1 and C-2 13C labeled
D-glucose. The proposed mechanism involves an isomerization
of D-glucose to D-fructose via open chain forms during the
dehydration reaction.645
In a related example, one-pot conversion of lignocellulosic
and algal biomass into a liquid fuel 2,5-dimethylfuran (DMF)
has been achieved by using a multicomponent catalytic system
Figure 33. Brönsted acidic ionic liquid catalyzed transformation of D-fructose to 5-hydroxymethylfurfural (HMF).
6157
Review
comprising acidic ionic liquid N,N-dimethylacetamide meth-
anesulfonate, Ru/C, and formic acid as shown in Figure 34.658
Figure 34. One-pot conversion of lignocellulosic and algal biomass
into 2,5-dimethylfuran (DMF)658
Cellulose can be depolymerized to glucose and then
dehydrated to HMF in one-pot using acidic ionic catalysts.659
Ding et al. reported the catalytic conversion of microcrystalline
cellulose (MCC) to HMF using CuCl2 in 1-(4-butylsulfonic)-3-
methylimidazolium hydrogen sulfate [(HSO 3) 4C4 C1 im]-
[HSO4] in 69.7% yield.660 In an example using raw biomass,
the carbohydrate-rich weed species foxtail weed was directly
converted to platform chemicals HMF and 5-ethoxymethyl-2-
furfural using dimethylacetamide methanesulfonate and N-
methylpyrolidinium methanesulfonate as catalysts giving HMF
in 58 and 52% yields, respectively.661
In the C5 sugar platform, Serrano-Ruiz et al. reported the
dehydration of xylose to furfural using −SO3H functionalized
acidic ionic liquids under microwave heating.662 In another
example, Tao and co-workers reported the 1-(4-butylsulfonic)-
3-methylimidazolium hydrogen sulfate [(HSO3)4C4C1im]-
[HSO4] catalyzed dehydration of xylose into furfural under
mild conditions. A xylose conversion of 95.3% with a furfural
yield of 91.45% was achieved in a 25 min reaction time at 150
°C.663
4-Oxopentanoic acid or levulinic acid is a renewable
generation key chemical that can be derived from C5 and C6
carbohydrates via a series of dehydration/hydration reactions
and acidic ionic liquids have been used as catalysts for the
preparation of levulinic acid and related compounds. High
molecular weight cellulose has been converted to a mixture of
ethyl levulinate and levulinic acid by using 1-(3-propylsulfonic)-
3-methylimidazolium chloride [(HSO3)3C3C1im][Cl] as the
catalyst in aqueous ethanol medium in a one-pot operation
under mild conditions as shown in Figure 35.664 The highest
ethyl levulinate yield of 19.0% was obtained for a reaction
carried out at 170 °C, for 12 h, in water−ethanol medium
containing 38.5% water. The levulinic acid yields continues to
increase with increasing water content up to about 54% water
in aqueous ethanol for reactions carried out at 150 °C for 48 h,
and the highest levulinic acid yield was 23.7%. The BAIL
catalyst could be efficiently recovered (96%) from the water
phase with negligible contamination and the stability of the
catalyst was confirmed by comparison of the 1H NMR
spectrum of the recovered catalyst with fresh catalyst.664
In another example cellulose has been liquefied in ethylene
glycol at 180 °C, using 6.7 mol % 1-(3-propylsulfonic)-3-
methylimidazolium chloride [(HSO3)3C3C1im][Cl] and 1-(4-
butylsulfonic)-3-methylimidazolium hydrogen sulfate
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Figure 35. Brönsted acidic ionic liquid 1-(3-propylsulfonic)-3-methylimidazolium chloride [(HSO3)3C3C1im][Cl] catalyzed conversion of cellulose
to 5-hydroxymethylfurfural (HMF), levulinic acid (LA), and ethyl levulinate (EL) in water−ethanol solvent system.664
[(HSO3)4C4 C1im][Cl]. The liquefied oil produced contained
only three compounds as shown in Figure 36, which were
Figure 36. 1-(3-Propylsulfonic)-3-methylimidazolium chloride
[(HSO3)3C3C1im][Cl] and 1-(4-butylsulfonic)-3-methylimidazolium
hydrogen sulfate [(HSO3)4C4 C1im][Cl] catalyzed liquefaction of
cellulose in ethylene glycol.
identified as 2-hydroxyethyl levulinate, 2-hydroxyethyl levuli-
nate ethylene ketal, and 2,3,6,7-tetrahydro-cyclopenta[1,4]-
dioxin-5-one.665 The composition of the three components
reaches a steady state after 20 h reaction at 180 °C with 2-
hydroxyethyl levulinate: 2-hydroxyethyl levulinate ethylene
ketal: 2,3,6,7-tetrahydro-cyclopenta[1,4]dioxin-5-one molar
percentage ratio of approximately 47:22:31.665
Figure 37. Application of acidic ionic liquids in liquefaction of sawdust in polyethylene glycol 400-glycerol mixtures668
6158
Review
The catalytic performances of AIL containing HSO4− anion
and acidic functionalized imidazolium cations have been
investigated for biomass liquefaction in polyethylene glycol
400-glycerol mixtures as well as in monohydric alcohol like 1-
octanol666,667 in order to explore green and efficient ways to
convert woody biomass into sustainable energy and chemicals
as shown in Figure 37. These results showed that fir sawdust
could be liquefied up to 99% using 0.3 mol·L−1 1-(3-
propylsulfonic)-3-methylimidazolium chloride as the catalyst
at a temperature of 423 K, in 60 min. Furthermore, Lu and co-
workers reported that more than 90 wt % of the bio-oil was the
heavy oil that derives from lignin.668
Single reactor conversion of lignocellulosic biomass to C5−
C20 furanic biocrude oils using sulfonic acid functionalized
Brönsted acidic ionic liquid catalysts is another application of
BAILs.664 In this biomass liquefaction untreated switch grass
was liquefied to a mixture of biomass derived furan-acetone
aldol condensation products using [(HSO3)3C3C1im][Cl] or
[(HSO3)4C4C1im][Cl] as the BAIL catalyst under moderate
temperature−pressure conditions.669 As described earlier there
are numerous examples of applications of acidic ionic liquids in
the preparation of levulinic acid and related biomass derived
compounds, some selected examples and their references are
shown in Table 18.
9.7.2. Depolymerization of Cellulose. Ionic liquids with
built-in −SO3H acid functionality is an emerging class of
biomass processing systems,676 whereas relatively milder acidic
ionic liquids like 1-butyl-3-methylimidazolium hydrogensulfate
are used in partial depolymerization and preparation of
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Table 18. Selected Examples of Application of Acidic Ionic Liquids in Preparation of Levulinic Acid and Related Biomass Based
Compounds
preparation of levulinic acid
acidic ionic liquid catalyst(s) and related compounds. refs
[(HSO3)3C3C1im][HSO4], [(HSO3)4C4C1im][HSO4], [(HSO3)3C3C1im][Cl], [(HSO3)3C3C1im] cellulose → levulinic acid hydrothermal670 and
[H2PO4], [(HSO3)3C3C1im][OMs], [(HSO3)3C3(C2)3N][HSO4], [(HSO3)3C3Py[HSO4] and microwave
[(HSO3)3C3Ph3P][HSO4] conditions671
[C4C1im][HSO4] bamboo shoot shell → 672,673
levulinic acid
[(HSO3)4C4C1im][HSO4] furfural + ROH (MeOH, 674
EtOH, nBuOH and iPrOH)
→ levulinate esters
[(HSO3)4C4C1im][HSO4] cellulose + butanol → butyl 675
levulinate
[((HSO3)3C3)2im][HSO4] furfural alcohol → alkyl 320
levulinates

cellulose nanowhiskers.677 These Brönsted acidic ionic liquids Table 19. Average % Yields of TRS and Glucose Produced in
can behave as the solvent as well as the catalyst; additionally, no 10% w/w Cellulose in Brönsted Acidic Ionic Liquid
neutralization and separation of the acid catalyst is required, Solutionsa
and there is no waste in acid, as the acid is in the solvent itself.
temp. (°C)/time
Furthermore, a higher concentration of −SO3H active sites is (min) yield (%)
expected to accelerate the reaction and lower the operating
before after
temperature, thus saving energy. In March 2015 da Costa adding adding
Lopes and Bogel-Łukasik published a review article with 131 entry BAIL/cellulose H2O H2O TRS glucose
references on perspectives of hydrolysis and conversion of 1 [(HSO3)3C3C1im][Cl] /α- 70/60 70/30 59 15
cellulose and lignocellulosic biomass using acidic ILs, justifying cellulose
the fast growth in the field.77 2 [(HSO3)3C3C1im][Cl]/ 70/60 70/30 12 4
MC-cellulose
The first use of this class of Brönsted acidic ionic liquids were
3 [(HSO3)3C3C1im][Cl]/ 70/60 70/30 62 14
reported by Amarasekara and Owereh in 2009.678 In this work Sigmacell
they reported that cellulose rapidly dissolves in Brönsted acidic 4 [(HSO3)3C3C1im][Cl]/ 70/30 39 12
ionic liquids 1-(3-propylsulfonic)-3-methylimidazolium chlor- Sigmacell
ide and 1-(4-butylsulfonic)-3-methylimidazolium chloride up to 5 [(HSO3)3C3C1im][Cl]/ 70/40 70/30 56 12
20 g/100 g ionic liquid by gentle mixing at room temperature. Sigmacell
Optical microscope images (x 400) of dissolution of Sigmacell 6 [(HSO3)3C3C1im][Cl]/ 70/60 70/60 42 7
Sigmacell
cellulose (DP ≈ 450) are shown in Figure 38.678 7 [(HSO3)3C3C1im][Cl]/ 70/60 70/240 29 4
Sigmacell
8 [(HSO3)3C3C1im][Cl]/ 50/960 32 3
Sigmacell
9 [(HSO3)3C3C1im][Cl]/ 90/30 34 3
Sigmacell
10 [(HSO3)3C3C1im][Cl]/ 90/30 90/30 26 2
Sigmacell
11 [(HSO3)3C3C1im][Cl]/ 90/240 15 2
Sigmacell
12 [(HSO3)4C4C1im][Cl]/α- 70/60 70/30 32
cellulose
13 [(HSO3)4C4C1im][Cl 70/60 70/30 7
]/MC-cellulose
Figure 38. Optical microscope images (×400) of dissolution of
14 [(HSO3)4C4C1im][Cl]/ 70/60 70/30 12
Sigmacell cellulose (DP ≈ 450) in 1-(3-propylsulfonic)-3-methyl- Sigmacell
imidazolium chloride at room temperature (23 °C) and atmospheric 15 [(HSO3)4C4Py][Cl]/α- 70/60 70/30 14
pressure, after 0, 60, and 150 s. Reprinted with permission from ref cellulose
678. Copyright 2009 American Chemical Society. 16 [(HSO3)4C4Py][Cl]/MC- 70/60 70/30 8
cellulose
17 [(HSO3)4C4Py][Cl]/ 70/60 70/30 16
Hydrolysis of cellulose was tested with three cellulose-ionic Sigmacell
liquid systems with imidazolium, pyridinium and triethanol 18 [(HSO3)4C4(HO2C2)3N] 70/60 70/30 5
[Cl] /α-cellulose
ammonium cations by the addition of 2.0 equiv of water per
19 [(HSO3)4C4(HO2C2)3N] 70/60 70/30 2
glucose unit of cellulose and heating the solution at 70 °C, and [Cl]/MC-cellulose
at atmospheric pressure with or without preheating to give 20 [(HSO3)4C4(HO2C2)3N] 70/60 70/30 10
glucose along with other reducing sugars. The average % yields [Cl]/Sigmacell
of total reducing sugar (TRS) and glucose produced in a series a
2.0 equiv of H2O per glucose unit of cellulose were added in all
of cellulose hydrolysis experiments using Brönsted acidic ionic hydrolysis experiments678.
liquids are shown in Table 19. Hydrolysis of Sigmacell cellulose
(DP ≈ 450) in 1-(3-propylsulfonic)-3-methylimidazolium glucose (14%) yields, and was attained with 1 h. of preheating
chloride produced the highest total reducing sugar (62%) and at 70 °C and 30 min heating at 70 °C, after adding water.
6159 DOI: 10.1021/acs.chemrev.5b00763
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Chemical Reviews
Table 20. Selected Examples of Application of Acidic Ionic Liquids in Hydrolysis of Cellulose and Cellulosic Biomass
acidic ionic liquid catalyst(s)
1-propyl sulfonic acid-2-phenyl imidazoline hydrogensulfate and 1- butyl sulfonic acid-2-
phenyl imidazoline hydrogensulfate
[(HSO3)3C3C1im][HSO4], [(HSO3)3C3C1im][OTs] and [(HSO3)3C3C1im][Cl]
[(C1Him][Cl]
[(HSO3)3C3(C2)3N][HSO4]
[(HSO3)4C4C1im][HSO4]
[(HSO3)3C3C1im][Cl] immobilized on silica
[(HSO3)3C3(CC)im][OTf] polymer
[(HSO3)4C4C1im][Cl]
1,1,3,3-tetramethylguanidinium hydrogensulfate
[(HSO3)3C3C1im][Cl] immobilized on polystyrene
[(HSO3)3C3C1im][Cl] and [(HSO3)4C4C1im][Cl]
[(HSO3)4C4N2(CH2)3]3−nHnPW12O40
[(HSO3)3C3C1im][HSO4].1/3Cr
[(HSO3)3C3C1im][Cl] immobilized on biochar with ZnCl2 and CuCl2
Later, Liu et al. as well as Feng et al. also reported the use of
Brö nsted acidic ionic liquids for catalysis of cellulose
depolymerization under mild conditions.679,680 However, their
approach is somewhat different from the earlier group, where
Liu et al. first dissolved cellulose in the neutral ionic liquid
1-nbutyl-3-methylimidazolium chloride to make a 5% solution,
and then Brönsted acidic ionic liquid and a controlled amount
of water was added to hydrolyze cellulose. Furthermore, a series
of −SO3H group functionalized imidazolium and triethylam-
monium Brönsted acidic ionic liquids were used as catalysts in
the Liu et al.’s study.679 They found that all of the Brönsted
acidic ionic liquids studied are effective in hydrolysis of
cellulose, with the maximum total reducing sugar (TRS) yields
over 83% at 100 °C. Acidic ionic liquids with analogous
structures showed similar catalytic activities and (3-propylsul-
fonic)-triethylammonium hydrogen sulfate showed the highest
activity in this study. Interestingly, acid group functionalized
acidic ionic liquids can be used as catalysts in aqueous media as
well under moderately high temperature−pressure conditions
with or without a cocatalyst. Amarasekara and Wiredu studied
the catalytic activities of dilute aqueous solutions of 1-(3-
propylsulfonic)-3-methylimidazolium chloride for the hydrol-
ysis of pure cellulose by comparison with p-toluenesulfonic acid
and sulfuric acid.681 In this study dilute aqueous solutions of 1-
(3-propylsulfonic)-3-methylimidazolium chloride and p-tolue-
nesulfonic acid are shown to be better catalysts than aqueous
sulfuric acid of the same H+ ion concentration for the
degradation of cellulose at moderately high temperatures and
pressures. For example, Sigmacell cellulose (DP ∼ 450) in
aqueous solutions of 1-(1-propylsulfonic)-3-methylimidazolium
chloride, p-toluenesulfonic acid, and sulfuric acid of the same
acid strength (0.0321 mol H+ ion/L) produced total reducing
sugar (TRS) yields of 28.5, 32.6, and 22.0% respectively, after
heating at 170 °C for 3.0 h. In the same set of experiments 22.2,
21.0, and 16.2% glucose yields were attained in 1-(1-
propylsulfonic)-3-methylimidazolium chloride, p-toluenesul-
fonic acid, and sulfuric acid mediums, respectively.681 In
addition, hydrolysis of a cellulose model compound in water
also supported the observation of enhanced catalytic activity of
−SO3H functionalized imidazolium BAILs in water in
comparison to H2SO4.682 Structure−activity relationships in a
6160
Review
hydrolysis of polysaccharide/biomass and conditions refs
cellulose, 100 °C, 60 min. 85.1% TRS yield 687
hardwood hemicellulose, 160 °C to give C5 sugars (xylose + 688
arabinose) in 87% yield
soybean straw and corn straw, 70 °C, 120 min. 689
cellulose, 100 °C, 99% TRS yield 679
cellulose, sawdust, 80−120 °C 690,691
cellulose, 70 °C, glucose and TRS in 26 and 67% yields 225
respectively
cellulose, 100 °C, 77% yield 692
switchgrass, 70 °C for 2 h, 58. One %TRS and 15. Three % 693
glucose yields
cellulose, 26% glucose and 72% TRS yields 694
cellulose, 160 °C, 3 h, glucose, TRS in 21.7 and 50.1% yields 282,695
respectively
cellulose, 140−180 °C, 3 h 683
cellulose 696
cellulose, 94% TRS yield 695
cellulose and bamboo 697,698
series of −SO3H functionalized imidazolium, pyridinium,
trialkylammonium BAILs have revealed that single −SO3H
attached imidazolium catalysts are more effective than
pyridinium and trialkylammonium types in cellulose hydrolysis
in water at moderate temperature−pressure conditions.683 A
number of research groups have studied acidic ionic liquids
immobilized on a solid supports, which include; graphene-like
nanoporous carbons,684 silica,225,233 and polystyrene282 for the
depolymerization of cellulose as well as various lignocellulosic
biomass forms.
Acidic ionic liquid catalysts have been tested for liquefaction
of untreated lignocellulosic biomass samples as well, and these
experiments often produced complex mixtures of products.
Long and co-workers used a −SO3H, −COOH functionalized,
and HSO4-paired imidazolium ionic liquid as catalysts for
bagasse liquefaction in hot compressed water. Using −SO3H
functionalized ionic liquid at 542 K, 96.1% of bagasse could be
liquefied and 50.6% was selectively converted to low-boiling
biochemicals.685 In another experiment a series of AILs
containing HSO4− and imidazolium cation were used in the
liquefaction of Chinese fir sawdust in 1-octanol. This
experiment showed that the liquefaction rate could be gradually
improved with the AILs of increasing acidity, and reached
71.5% when 1-(4-butylsulfonic)-3-methylimidazolium hydro-
gen sulfate was used as the catalyst at 423 K, with the 6:1 mass
ratio of 1-octanol to sawdust.667 Zhuo et al. recently reported
the synthesis of a series of 2-phenyl-2-imidazoline based acidic
ionic liquids and used as catalysts for the hydrolysis of cellulose
in 1-butyl-3-methylimidazolium chloride.686 They noted that
BAILs with anions HSO4− and Cl− showed better catalytic
performance for the hydrolysis of cellulose than those with
H2PO4−.686 Selected recent examples in the hydrolysis of
cellulose and cellulosic biomass using acidic ionic liquids are
shown in Table 20.
The addition of some metal ions699−701 and zeolites702 as
cocatalysts are also known to enhance the BAIL catalyzed
hydrolysis of cellulose in neat and in aqueous media. In a recent
development the effect of eight metal ions, Cr3+, Mn2+, Fe3+,
Co2+ Ni2+, Cu2+, Zn2+, and La3+ on 1-(1-propylsulfonic)-3-
methylimidazolium chloride acidic ionic liquid catalyzed
hydrolysis of cellulose in water at 140−170 °C was reported.700
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Table 21. Recent Applications of Acidic Ionic Liquids in Biodiesel Synthesis
acidic ionic liquid catalyst(s)
[C4C1im][HSO4] and [C4C1im][OTf]
[(HSO3)3C3(CC)im][H2PO4] polymer
[(HSO3)3C3C1im][HSO4] immobilized on magnetic nanoparticles
[(HSO3)4C4C1im][HSO4] -Fe2(SO4)3
[(HSO3)4C4C1im][Cl]
3-butyl-6-sulfo-1-(4-benzylsulfonic)-1H-imidazolium hydrogen sulfate
[(HSO3)3C3pyr][HSO4] immobilized on polymer
[(HSO3)4C4 (alkyl)im][OTf] immobilized on silica
[(HSO3)3C3(C2)3N][Cl].0.67FeCl3
[(HSO3)4C4C1im][HSO4], [(HSO3)3C3C1im][HSO4] and 1-methyl-2-(4-butylsulfonic)-
pyrazolium hydrogensulfate
[(HSO3)3C3(C2)3N][HSO4]
[(HSO3)4C4pyr][HSO4]
[(C2)3HN][HSO4] and [C4Him][HSO4]
It is interesting to note that certain transition metal ions like
Mn2+, Fe3+, and Co2+ as cocatalysts produced significant
enhancements in total reducing sugar (TRS) yields, with Mn2+
showing the highest activity. During these BAIL catalyzed
cellulose hydrolysis in water, using Mn2+ as cocatalyst produced
91.8, and 91.9% TRS yields, whereas samples without Mn2+
gave 28.0 and 28.7% yields at 160 and 170 °C, respectively.700
9.7.3. Depolymerization of Lignin. In addition to the
hydrolysis of polysaccharide components acidic ionic liquids
have been used as acid catalysts for the depolymerization of
lignin fraction in a number of biomass materials. Ekerdt and co-
workers separated the lignin from Oak wood by dissolving in
the neutral ionic liquid 1-methyl-3-ethylimidazolium acetate
and subsequent precipitation. This was successfully depoly-
merized in the acidic ionic liquid 1-H-3-methylimidazolium
chloride under mild conditions (110−150 °C).703 Furthermore,
gel permeation chromatography results, showed that an
increase in temperature from 110 to 150 °C increased the
rate of reaction, but did not significantly change the final size of
the lignin fragments.703 In model compound studies, the same
research group showed that β-O-4 bonds of both guaiacylgly-
cerol-β-guaiacyl ether and veratrylglycerol-β-guaiacyl ether
undergoes catalytic hydrolysis to produce guaiacol as the
primary product with more than 70% yield at 150 °C.704,327
Long and co-workers examined the liquefaction of sugar cane
bagasse lignin using acidic ionic liquid 1-(4-butylsulfonic)-3-
methyl imidazolium hydrogen sulfate [(HSO3)4C4C1im]-
[HSO4]. They showed that more than 65% of liquefaction
can be achieved under optimized conditions, yielding 13.5% of
useful aromatic fine chemicals such as phenol, 4-ethylphenol,
and guaiacol.705
9.7.4. Pretreatment of Biomass. Pretreatment of biomass
as a preparation for enzymatic hydrolysis is another application
of acidic ionic liquids. In this application dilute aqueous
solutions of acidic ionic liquids are often used under mild
conditions. The selective hydrolysis of hemicellulose fraction is
known in using BAIL based pretreatments.706 Cox and Ekerdt
have shown that acidic ionic liquid 1-H-3-methylimidazolium
chloride can be used for effective pretreatment of yellow pine
wood chips under mild conditions.707 In this study wood
samples were treated between 110 and 150 °C for up to 5 h in
the ionic liquid and three fractions were collected; a cellulose
rich fraction, lignin, and an aqueous fraction. This treatment
caused the hemicellulose and the lignin to be degraded and
dissolved from the cell walls of the pine wood. The lignin was
6161
Review
starting material, biodiesel % yield refs
waste cooking oil, 95.65%. Sewage sludge 713,714
lipids, 90%
vegetable oil, 94.2% 220
soybean oil with short-chain alcohols 239
Camptotheca acuminata seed oil, 95.7% 189
jatropha curcas oil, 93.9% 715
Nigella sativa seed oil with methanol 716
waste cooking oil, 99.0% 215,213,214
glycerol trioleate with methanol 227
waste cooking oil, 95% 192
soybean oil and citrullus colocynthis oil 717−719
soybean oil with methanol, 93.2% 720
soybean oil and methanol, 94.5% 721
palm oil 722,723
depolymerized and subsequently dissolved in the ionic liquid.
This process occurred more quickly at higher temperatures,
although at the highest temperatures tested significant cellulose
degradation also occurred.707 Then there are few other biomass
forms that have been tested with aqueous acidic liquid
pretreatments, which include pretreatment of corn stover
using [C1C2im][HSO4],171 microalgae using n-butyl-3-methyl-
imidazolium hydrogen sulfate,708 hybrid aspen and Norway
spruce using [C1C4im][HSO4],709 and microwave pretreatment
of eucalyptus [C1C4im][HSO4].710
9.8. Biodiesel Synthesis
Biodiesel is the fatty acid methyl ester product formed by trans-
esterification of vegetable oils or animal fats with methanol. The
trans-esterification reaction can be catalyzed by bases or
acids.711 A fair number of researchers have studied the option
of using homogeneous and immobilized forms of Brönsted
acidic ionic liquid catalysts for this trans-esterification reaction
due to possibilities like low catalyst loading and recycling of the
catalyst. In 2012 Amin, Fauzi and Hafiidz published a review
article titled “An overview of ionic liquids as solvents in
biodiesel synthesis” with 138 references summarizing the
progress in this area until late 2011.712 More recent and after
2012 applications of acidic ionic liquids in biodiesel synthesis
are shown in Table 21.
9.9. Desulfurization of Gasoline, Diesel, and Petroleum
Refinery Applications
The removal of cyclic sulfur compounds and nitrogen
compounds such as thiophene (TS), dibenzothiophene
(DBT), carbazole, pyridine, and their derivatives from gasoline
and other fuel oils is another application in acidic ionic
liquids.212,724−726 A number of common Brönsted and Lewis
acid ionic liquids have been tested for hydrodesulfurization and
hydrodenitrogenation processes, which includes dialkylpyridi-
nium tetrachloroferates and [C1C6im][FeCl4],727,728 1-methyl-
imidazolium hydrogen sulfate [C1Him][HSO4], N-methylpyr-
rolidinium hydrogen sulfate [C1HPyrr][HSO4],729 [C1C4im]-
[HSO4],730,731 [(HSO3)2C2C1im][HSO4].732,733 N-methyl-
pyrrolidonium tetraflouoroborate [C 1 HPyrr][BF 4 ], 734
[C4C1im][FeCl4],735 and [(COO)C1C1im][HSO4].382
Chen and co-workers demonstrated that Lewis acidic ILs 1-
butyl-3-methylimidazolium chloride with IL: ZnCl2 1:1 and 1:2
mol ratios as well as Brönsted acidic ILs [C4C1im][HSO4] and
[C4C1im][HSO4], Lewis-Brönsted acidic IL N-methylpyrroli-
donium zinc chloride with IL: ZnCl2 mole ratios 2:1 to 1:2 can
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be used to extract thiophene, dibenzothiophene, carbazole, and Table 22. Electrodeposition of Metals Using Lewis Acidic
pyridine from their hexane (model gasoline) or octane (model Ionic Liquids with Halometalate Anions
diesel fuel) mixtures. Typically, 93.8% TS removal (S-content
electrodeposition/
drops from 500 to 31 ppm) and 95.9% DBT removal (S- acidic ionic liquids electroplating metal/alloy refs
content from 516 to 21 ppm) by [C4C1im][ZnCl3] are [C2C1im][AlCl4] Al on a Mg alloy 752−755
achieved after 6-stage extraction at 25 °C; while 93.8% AlInSb semiconductor
carbazole removal (N-content from 279 to 17 ppm) and alloys
97.8% pyridine removal (N-content from 495 to 11 ppm) were [C2C1im][AlCl4] Al and Zn on AZ91D 756,757
realized just after one stage extraction and the N-content is magnesium alloy
undetectable after 2-stage extraction.736,187,737 In another [C4C1im][AlCl4] Pb on Au 758
experiment using a series of FeCl3-containing 1-hexyl-3- [C2C1im][ZnCl3] - NiCl2 NiZn nanofilaments on W 759
methylimidazolium chloride Lewis-acidic ionic liquids the [C1(CC)im][AlCl4] and Al, 760,761
[C4C1im][AlCl4]
selectivity of sulfur compounds by extraction process followed
[C2C1im][AlCl4] - K3[W2Cl9] Al−W alloy 618,617,616
the order of dibenzothiophene (DBT) > benzothiophene (BT) [C8C1im][GaCl4] Ga 619
> 4,6-dimethyldibenzothiophene (4,6-DMDBT).738 [(C1)3HN][AlCl4] Al wires 614
9.10. Metal Extractions and Processing [C4C1im][ZnCl3] and Zn and Zn−Cu alloy 762,763
[C2C1im][ZnCl3] - CuCl
In the last 5−6 years a fair number of research groups have [C2C1im][AlCl4] Ternary Al−W−Mn alloys 764
explored the use of ionic liquids for the extraction and [C2C1im][AlCl4] - MgCl2 Al−Mg alloys on to Pt and 765
processing of metals and particularly rare earth metals.739−741 Cu
Among the ionic liquids used in this applications, there are [C4Py][AlCl4] - NiCl2 Al−Ni alloys on to Pt and 89
protic ionic liquids and carboxyl acid group functionalized ILs. mild steel
The representative examples are the use of protic ionic liquids [C2C1im][AlCl4] - HfCl4 Al−Hf alloys onto Cu 766
trioctylammonium bis(trifluoromethanesulfonyl)amide in the
extraction of Pd and Pt,742 carboxyl-functionalized ionic liquid:
In an electrochemical etching study, anodic behavior of Mg
betainium bis(trifluoromethylsulfonyl)imide, for a combined
in 1-ethyl-3-methylimidazolium chloride-AlCl3 ionic liquid was
leaching/extraction of Nd from a neodymium−iron-boron
investigated by Xu and co-workers.767 During this experiment
magnets (NdFeB) in the recycling process,743 mixtures of
dissolution of Mg under anodic polarization occurred after the
trioctylammonium bis(trifluoromethanesulfonyl)amide and tri-
breakdown of the oxide film and a formation of a viscous layer
octylammonium nitrate for the extraction of aluminum(III),
was observed at the Mg-ionic liquid interface during the
gallium(III), and indium(III) from hydrochloric acid solu- dissolution process.
tions.744 In addition immobilized AILs have been used in
selective absorption and removal of Cr6+ as well.237 9.12. Miscellaneous Applications of Acidic Ionic Liquids
The protic ionic liquids have been used to extract metal ions In addition to the AIL applications discussed, the oxygen
by leaching from metal ores. Dong et al. used an aqueous reduction reaction has been studied at platinum, gold, and
solution of 1-butyl-3-methylimidazolium hydrogensulfate for glassy carbon electrodes using cyclic voltammetry and
the leaching of chalcopyrite concentrate at ambient pressure at potential-step chronoamperometry in 11 room temperature
50 to 90 °C in air. The copper extraction increased from 52% protic ionic liquids.768 Protic chiral ionic liquids based on
to 88% as the ionic liquid concentration in solution increased ephedrines have been used in chiral recognition. Interestingly
from 10% (v/v) to 100%. Copper extraction was very low at ephedrinium protic chiral ionic liquids displayed strong chiral
temperatures below 70 °C, but increased significantly at recognition capabilities as evidenced by peak splitting in the
19
temperatures from 70 to 90 °C, suggesting a high activation F-NMR spectrum of the Mosher’s salt. In addition, these
energy for the chemical reaction.745 Recovery of zinc and protic chiral ionic liquids demonstrated enantiomeric recog-
copper with the BAIL as leachate is another recent nition capabilities toward a range of structurally diverse analytes
application.746−748 In experiments with brass waste it was as well.369 The use as a structure directing media is another new
found that all zinc in brass waste could be dissolved using application of AILs, where 1-butyl-3-methylimidazolium hydro-
Brönsted ionic liquid 1-butyl-3-methyl-imidazolium hydro- gensulfate was used as an acidic, hydrolyzing and templating/
gensulfate. The metallic zinc could be recovered by the structure directing agent and where BAILs were used in the
electrowinning method without a purification step.746 synthesis of nanocrystalline anatase TiO2769 and shape-
controlled biochar materials.770
9.11. Electrodeposition of Metals
Electrodeposition or electroplating of metals is an important 10. CONCLUDING REMARKS
manufacturing process. In some metals, molten salts are The ionic liquid field has grown into a wide subject area in the
required in electrodeposition. In these cases the use of metal past decade, and acidic ionic liquid is an important branch in
containing low melting acidic ionic liquids as the electrolyte has this subject. The central theme of this review is to show the
certain advantages as these metalo ionic liquids have much structural diversity of AILs and to highlight the range of
lower melting points than metal salts and requires less energy in complex applications of acidic ionic liquids. The combination of
maintaining the liquid electrolyte. The most common type of acidic and ionic liquid properties into a single molecule has
ionic liquids used for this application are Lewis acidic ionic opened new opportunities. The most recent advancements in
liquids with halometallate anions, and some of the electro- using the new AILs appears to be in catalysis, lignocellulosic
deposition applications are described in the patent litera- biomass processing, and electrolyte applications. In the catalysis
ture.749−751 A selected list of electrodeposition of metals using area many organic reactions first discovered with mineral acids
acidic ionic liquids is presented in Table 22. like concentrated H2SO4 were later found to work better with
6162 DOI: 10.1021/acs.chemrev.5b00763
Chem. Rev. 2016, 116, 6133−6183
Chemical Reviews Review

organic soluble sulfonic acids like p-toluene sulfonic acid and
fluorinated super acids. Now the same reactions are being
tested again with BAILs and in many cases the BAILs have
shown superior catalytic properties in comparison to organic
sulfonic acids and mineral acids. This may be due to organic
soluble nature and interactions of charged intermediates with
cation/anion in BAIL that allows facile proton or electron
transfers with acidic ionic liquids.
The use of BAILs in biomass processing research is an
important turning point. The introduction of sulfonic acid
group functionalized acidic ionic liquids in the depolymeriza-
tion of cellulose in 2009 has opened a new branch of research
with a vast potential and industrial applications.678 The rapid
progress in this arena since the introduction of AILs in biomass
processing has been reviewed by da Costa Lopes and Bogel-
Łukasik in the March 2015 review titled “Acidic ionic liquids as
sustainable approach of cellulose and lignocellulosic biomass
conversion without additional catalysts”.77 The future of acidic
ionic liquids as biomass processing catalysts is bright, and one
possibility is the development of an ionic liquid based small
molecular mimic for cellulase enzyme. The BAIL catalyst has
the features of the enzyme; it can bind with cellulose via
hydrogen bonds, and if the orientation is correct it can deliver
the acidic proton to glycosidic bond of cellulose promoting the
hydrolysis, like the cellulase enzyme. However, a lot more work
is needed in the area of BAIL−cellulose binding mechanisms
using experimental and computational tools.
The second highlighted area is the ionic conductivity aspects
of acidic ionic liquids. The earliest known application of this
property is the use of Lewis acidic ionic liquids with metal salts
like AlCl3 for the electrodeposition of Al, which generally
require high melting salt baths without the use of ionic liquid
based systems. Then more recent developments are in ion
conducting membranes and electrolytes in fuel cells as well as
in batteries, and these uses are in the verge of commercial
applications.
Overall, acidic ionic liquids have grown onto their own sub
discipline with vast array of applications. Some of the research
in this area is geared toward technologies likely to replace the
use of noble metal on chlorinated alumina for reforming and
CoMo/NiMo catalysts for desulfurization of gasoline, by the
use of acidic ionic liquids as catalysts. Another possible
application is replacement of mineral acids in alkylation
processes. However, the cost of these new materials are much
higher than H2SO4 or HF; hence, the overall benefits of using
AILs depends on efficiency improvements as well as the
recyclability of AILs. The future of acidic ionic liquids in
industrial applications is promising as many indications have
shown the advantages AILs over traditional acids in numerous
processes.
AUTHOR INFORMATION
Corresponding Author
*E-mail: asamarasekara@pvamu.edu. Tel: +1 936 261 3107.
Fax: +1 936 261 3117.
Notes
The authors declare no competing financial interest.
Biography
Ananda S. Amarasekara is a professor of chemistry at Prairie View
A&M University in Texas, where he has been a faculty member since
2003. He received his B.Sc. degree from University of Colombo, Sri
Lanka, his Ph.D. in organic chemistry from City University of New
York (with William. F. Berkowitz, 1985), completed his postdoctoral
training at Bar-Ilan University in Israel (with Alfred Hassner, 1985-87),
and spent two years at the Center for Molecular Architecture at
Central Queensland University in Rockhampton, Australia as a visiting
scientist with Ronald Warrener. In 2009, professor Amarasekara’s
research group introduced the use of sulfonic acid group functionalized
Brönsted acidic ionic liquids for the direct hydrolysis of untreated
cellulose and lignocellulosic biomass to glucose and its oligomers. The
current research interests of his group are acidic ionic liquid based
catalysis and the development of chemocatalytic methods for the
processing of biomass to renewable fuels and feedstock chemicals. He
is the author of the book “Handbook of Cellulosic Ethanol” (Wiley -
Scrivener 2013) and has published more than 100 peer reviewed
research articles.
ACKNOWLEDGMENTS
Author thanks NSF Grants CBET-0929970, CBET-1336469,
and HRD-1036593 for financial support.
ABBREVIATIONS
AIL acidic ionic liquid
BAIL Brönsted acidic ionic liquid
DP degree of polymerization
DPA diphenolic acid
DTBP di tbutyl phenol
EL ethyl levulinate
HMF 5-hydroxymethylfurfural
LA levulinic acid
LAIL Lewis acidic ionic liquid
MEA mono ethanol amine
MPa mega Pascal
OBs benzenesulfonate
OTs toluene sulfonate
OTf trifluoromethanesulfonate
PAIL protic acidic ionic liquid
TBC tbutyl catechol
TBP tbutyl phenol
TEOS tetraethyl orthosilicate
Tfa trifluoroacetate
TOF turnover frequency
TON turnover number
TRS total reducing sugar
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