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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 Review

9.7.4. Pretreatment of Biomass 6161 Then, since 2006 there are five review articles published with
9.8. Biodiesel Synthesis 6161 the word “acidic ionic liquids” in the title.71−75 Of the more
9.9. Desulfurization of Gasoline, Diesel, and recent three reviews in this sub group; the article titled “Acidic
Petroleum Refinery Applications 6161 Brönsted ionic liquids” with 123 references was published in
9.10. Metal Extractions and Processing 6162 2010.73 The second with title “Structural effects on the
9.11. Electrodeposition of Metals 6162 physicochemical and catalytic properties of acidic ionic liquids:
9.12. Miscellaneous Applications of Acidic Ionic An overview” by Chiappe and Rajamani with 182 references
Liquids 6162 appeared in 2011.74 The most recent review titled “The use of
10. Concluding Remarks 6162 supported acidic ionic liquids in organic synthesis” with 79
Author Information 6163 references by Skoda-Foldes describes recent applications of
Corresponding Author 6163 acidic ionic liquids supported on organic and inorganic
Notes 6163 supports for catalysis applications.75 In addition a 2014 review
Biography 6163 titled “Halometallate ionic liquids-revisited” and a 2015 review
Acknowledgments 6163 titled “Acidic ionic liquids as sustainable approach of cellulose
Abbreviations 6163 and lignocellulosic biomass conversion without additional
References 6163 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
1. INTRODUCTION review on acidic ionic liquids is an attempt to cover all types of
Since the 1999 review titled “Room-Temperature Ionic acidic ionic liquids, their synthesis properties, and applications.
Liquids: Solvents for Synthesis and Catalysis” by Welton,1 It is important to define the nomenclature system used in
there are about a dozen books2−13 published with ionic liquids this acidic ionic liquid review at the introduction. As the
(ILs) in the title, and ionic liquids have grown in to a major number of ionic liquids and the number of research groups
research area in the last 15 years. A March 30th, 2016 search working on ionic liquids have proliferated, especially in the
using CAS SciFinder and Scopus for review articles with the neutral ionic liquid arena, there a number of deferent
keyword “Ionic liquids” in the title yielded 727 and 694 review abbreviations for ionic liquids in the literature. However, the
papers, respectively. As a number of previous reviews have system defined by Hallett and Welton for neutral ionic liquids
established the definition of ionic liquid as a salt in the liquid in their 2011 review article in “Chemical Reviews” is the widely
state, this review will also follow the same description. In some used system today.14 Despite this many articles in this area still
contexts, the term has been restricted to salts whose melting use their own abbreviations and naming systems, creating some
point is below some arbitrary temperature, typically 100 °C. confusion. Thus, it is about time to adopt a uniform
Thus, it is important to keep in mind the terms such as room- nomenclature for ionic liquids as in other well developed
temperature ionic liquid, molten salt, liquid organic salt, fused branches such as organometallic complexes. For instance most
salt, liquid electrolytes, ionic melts, ionic fluids, fused salts, and abbreviations used in the literature derive from the name of the
liquid salts have all been used to describe these salts in the ion; for example: [bmim]+ and [BMIM]+ both refer to the 1-
liquid phase. Since we have come a long way from the initial butyl-3-methylimidazolium cation. Nevertheless, there are
understanding of ionic liquids as nonvolatile solvents for ambiguities in this naming system, such as [pmim]+, which
reactions; today the subject area of ionic liquids is diverse and can be used for the 1-propyl-3-methylimidazolium cation as
wide, and it is impossible to analyze in a single review or a well as for the 1-pentyl-3-methyllimidazolium cation. To avoid
book. Hence, most recent reviews, book chapters, and books this complication, we have chosen to use an alphanumeric
are evaluating a branch, subgroup, or application in the general system to describe the alkyl chains, with an alphabetic
subject area of ionic liquids. abbreviation for the charged center. In this system the 1-
Numerous review articles on neutral ionic liquids can be butyl-3-methylimidazolium cation becomes [C4C1im]+. If the
referred to for information that is outside the scope of this alkyl chain is not linear, like for instance, the 1-tert-butyl-3-
article. These reviews have focused on a particular application methylimidazolium cation, it can be abbreviated as [tC4C1im]+.
of neutral nonfunctionalized or functionalized ionic liquids; for In the case of functionalized ionic liquids with a functional
example, chemical catalysis−solvents,14−26 biocatalysis,27−34 group in the side chain the type and position of the functional
chromatography and analysis,35−44 biomass pretreatment and group can be noted as well. In the case of an alcohol group on
processing45−50 electrochemical applications51−54,12,55−58 or the terminal carbon of the butyl chain, the abbreviation is
engineering fluids,59−62 and other miscellaneous applica- [(HO)4C4C1im]+, where the position of the OH group is
tions63−65,23,66−70 are covered in those articles. This review is shown as 4 as a superscript between the group and the attached
designed to give a comprehensive coverage of a selected class of carbon. Following this system described in the 2011 Hallett and
ionic liquids called acidic ionic liquids (AILs). An acidic ionic Welton’s review, this review extrapolates the same set of rules
liquid can be defined as a low melting ionic salt with acidic to functionalized class “acidic ionic liquids”. For example the
characteristics. The acidic character can be Brönsted, Lewis, or most widely described acidic ionic liquid 1-(3-propylsulfonic)-
a combination of Brönsted and Lewis acid type. Then the acidic 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
function(s) or group(s) can be either in the cation, anion, or [(HSO3)3C3C1im][Cl]. 1-(4-butylsulfonic)-3-methylimidazo-
both. The AILs are a part of a wider group of functionalized lium hydrogensulfate is [(HSO3)4C4C1im][HSO4]. Some
ionic liquids. As described above, it is important to note that common acidic ionic liquids and their nomenclature used in
the majority of the ionic liquids known and described in the this review are shown in Figure 1.
literature are neutral ionic liquids, and this review will The AILs with one acid function can be classified according
concentrate only the synthesis, properties, and applications to the type of acid function in the molecule. The Lewis acidic
the acidic subgroup. ionic liquids (LAILs) display their acidity due to a deficiency in
6134 DOI: 10.1021/acs.chemrev.5b00763
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Chemical Reviews 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
Figure 1. Common acidic ionic liquids. aluminum chloride to neutral ionic liquid organic chloride salt
[Cat]Cl, several negatively charged species are often present in
electrons, whereas Brönsted acidic ionic liquids (BAILs) display equilibrium. The formation of these chloroaluminate anions
their acidity due to ionizable protons. Then there are AILs with AlCl4¯, Al2Cl7¯, and Al3Cl10¯ are shown in the equations below:
more than one Brö nsted or Lewis acid function and
[Cat]Cl + AlCl3 ⇄ [Cat]AlCl4
combinations of Brönsted and Lewis acid functions as well.
[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. LEWIS ACIDIC IONIC LIQUIDS 2.1.2. Lewis Acidic Ionic Liquids with Zn, Sn, and
In the Lewis theory of acid−base reactions, the base donates a Other Metallic Anions. One main disadvantage of chlor-
pair of electrons and the acid accepts a pair of electrons. For oaluminate ionic liquids is their moisture sensitivity. The zinc
6135 DOI: 10.1021/acs.chemrev.5b00763
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based ionic liquids have been developed as a possible solution deposition,109 battery electrolytes, and as catalysts in Diels−
to this problem as well as a part of a search for lower melting Alder and Fisher indole synthesis.95,110
LAILs.94−97 The initial examples of these LAILs were produced The identification of various metal halide species in the metal
using zinc chloride with pyridinium, ethylphenylammonium,98 based LAILs is an important aspect in their studies and
and imidazolium salts.99−102 However, these LAILS showed applications. The most widely used techniques are FAB-mass
higher melting points than the corresponding chloroaluminate spectra and NMR spectroscopy. For example, three main
melts but are still fluids at ambient temperatures. During the chlorozincate anions in choline chloride (ChCl)/zinc chloride
same period it was also shown that FeCl2, FeCl3,103 and 1:2 composition ionic liquid have been identified as ZnCl3−
stannous salts104 form ionic liquids with 1-butyl-3-methylimi- (m/z 171), Zn2Cl5− (m/z 307), and Zn3Cl7− (m/z 443) by
dazolium chloride. FAB-mass spectra. In addition higher clusters are also
The continuous search for moisture stable LAILs with wider detectable at very low intensities. The formation of these
electrochemical applications led to the development of Zn and species can be explained in a series of equilibriums as shown in
Sn based quaternary ammonium type ionic liquids and the following equations:
especially salts such as choline chloride LAILs.94,105−108 The
melting behavior of mixtures of various ammonium salts with 2ZnCl 2 + Ch+Cl− ⇄ Zn2Cl5− + Ch+
zinc and tin chlorides is an interesting example; some of the
results from Davies and co-workers study are shown in Table 2Zn2Cl5− ⇄ ZnCl3− + Zn3Cl 7−
1.94 As revealed in this study; with salts of symmetrical cations,
Zn2Cl5− ⇄ ZnCl 2 + ZnCl3−
Table 1. Freezing Points for the LAIL Materials Formed In the case of Sn-based ionic liquids, FAB mass spectroscopy
from Heating a Quaternary Ammonium Chloride and MCl2 showed the presence of SnCl3− (m/z 225) and Sn2Cl5− (m/z
(M = Zn, Sn) in a 1:2 mol Ratio94 412). For the iron system the only anionic species detected was
cation M2+ freezing point/°C FeCl4− (m/z 197). Interestingly Sn3Cl7− or Fe2Cl7− clusters
+
could not be detected in Sn and Fe systems; most likely these
H4N Zn >200
species are too unstable to be observed using FAB-MS.105
Me4N+ Zn >200
NMR spectroscopy is another technique used in investigating
Et4N+ Zn 90−92
different species present in LAILs.111−115 Santini et al.
Me3N+Et Zn 53−55
examined the mixtures of ZnCl2 and 1-butyl-2,3-dimethyl
Me3N+CH2CH2OH Zn 23−25
imidazolium chloride [C4(C1)2im][Cl] using NMR and mass
Me3N+CH2CH2Cl Zn 23−25
spectrometry.116 In this study they found that [C4(C1)2im][Cl]
Me3N+CH2CH2OC(O)Me Zn 30−32
and [C4(C1)2im][ZnCl3] are present at χZnCl2 < 0.5 as well as
Me3N+CH2CH2OC(O)Ph Zn 46−48
pure [C 4(C 1 ) 2 im][ZnCl 3] at χZnCl2 = 0.5. Whereas a
Me3N+CH2CH2OH Sn 43−45
combination of [C4(C1)2im][ZnCl3] and [C4(C1)2im][Zn3Cl7]
Me3N+CH2CH2Cl Sn 69−71
was found at χZnCl2 > 0.5.116
Me3N+CH2CH2OC(O)Me Sn 13−15
Terrade and co-workers have investigated the anionic
Me3N+CH2CH2OH Zn/Sna 21−23
a
speciation of chlorostannate(II) LAILs, by 119Sn NMR
The ratio [Me3NCH2CH2OH]Cl:ZnCl2:SnCl2 was 1:1:1. 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,
H4NCl and Me4NCl, no liquid was formed below 200 °C, and differential scanning calorimetry. Both liquid and solid
whereas with the longer ethyl chain in Et4NCl the freezing systems (crystallized from the melt) contained [SnCl3]− in
point was 90 °C. The unsymmetrical ammonium salt Me3NEt+ equilibrium with Cl− in samples at χSnCl2 < 0.50; [SnCl3]− in
gave a freezing range of 53−55 °C, which is a reduction of 35 equilibrium with [Sn2Cl5]− at χSnCl2 > 0.50, and only [SnCl3]−
or 140 °C compared with Et4N+ and Me4N+ cations, at χSnCl2 = 0.50. In addition, Sn(II)chloride was found to
respectively. In addition, they found that functionalized ethyl precipitate when χSnCl2 > 0.63. Furthermore, the Lewis acidity
chains such as Me3N+C2H4Y give even lower freezing points; of the Sn(II)chloride based systems expressed by their
for example, if Y = OH or Cl, truly room temperature ionic Gutmann acceptor number has been determined as a function
liquids are observed with freezing points in the 23−25 °C of the composition χSnCl2, to reveal that Lewis acidity for χSnCl2
range. Even when the substituent is significantly larger, for > 0.50 samples are comparable to the analogous systems based
instance, Y = OC(O)Me or OC(O)Ph, the salts formed have on zinc(II). Furthermore, it was possible to estimate the change
lower freezing points than for Me3N+Et salt. These results in the Lewis basicity of the anion using 1H NMR spectroscopy,
suggest that both lower symmetry and the presence of a by comparison of the chemical shifts of the C-2 hydrogen in the
functional group may reduce the freezing points of the salts imidazolium ring. Finally, compositions containing free chloride
formed, though the exact role of the functional substituent is anions (χSnCl2 < 0.50) were found to oxidize slowly in air to
not yet clear. In all cases the liquids formed are viscous and form a chlorostannate(IV) ionic liquid containing the [SnCl6]2−
hygroscopic but moisture-stable, so these materials can be easily anion.114
prepared and stored without the need for special equipment.105 In another example Lungwitz and Spange studied the
The Zn and Sn containing choline based LAILs are a hydrogen-bond-accepting (HBA) and donating (HBD) param-
particularly attractive group in ammonium salts as they are eters of LAILs with halogeno complex anions by 1H NMR
water and air insensitive. In addition, they are easy to prepare spectroscopy.112 The imidazolium cation served both as part of
and relatively inexpensive, enabling their use in large-scale the LAIL and as a 1H NMR probe. The HBA and HBD
applications. The choline based zinc halide ionic liquids have strengths were calculated in terms of the empirical polarity
been used in numerous applications including zinc alloy parameters β and α according to the Kamlet−Taft equation.
6136 DOI: 10.1021/acs.chemrev.5b00763
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Chemical Reviews Review

The study included 1-butyl-3-methylimidazolium ionic liquid the replacement of chlorides with bromides leads to a similar
with chloroaluminates of various mole fractions from 0 to 0.67 tendency toward ionic diffusion. It would seem that ion
of AlCl3. The 1H NMR chemical shift of the C-2 proton in the association is less pronounced in the FeBr4− salts, which could
imidazolium cation was found to be dependent on the HBA be rationalized on the basis of a more significant nephelauxetic
ability of the corresponding anion. For the chloroaluminates effect together with the lower molar concentration in the FeBr4
the HBA ability decreased and the HBD ability increased with salts.137
increasing mole fraction of the Lewis acid. In general, the HBA 2.2. Lewis Acidic Ionic Liquids with Electron Accepting
strength of the LAILs studied increased in the following order: Ability in the Cation
MoCl6− < Al2Cl7− < AlCl4− < WCl7− < I5− < SnCl5− < I3− <
Lewis acidic ionic liquids with electron accepting ability in the
SbCl6− < TiCl5− < BBr4− < SnCl3−. The corresponding HBD
cation is not common in LAILs and a preparation of a boron
ability showed a reverse trend.112
containing example is shown in Figure 3.138
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 Figure 3. Synthesis of LAILs with electron accepting ability in the
solvents and acids.111 cation.
A few studies reported the X-ray structures of LAILs,114
where Zhou and Sasaki reported structures of several metal 3. BRÖ NSTED ACIDIC IONIC LIQUIDS
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 The Brönsted acidic property of a substance is based on the
interesting correlation between the symmetry of the metal- Brönsted−Lowry theory proposed independently by Johannes
containing anions and the melting points of the investigated Nicolaus Brönsted and Thomas Martin Lowry in 1923.
ILs, for a series of LAILs with the same cation and molar ratio According to this theory Brönsted acid is a substance that
of anion to cation (1:2),117 where they found that melting donates a hydrogen ion (H+) or proton. Brönsted base is a
points decreased in the order Oh > D4h > Td > D2d > C2v.117 substance that accepts a hydrogen ion (H+) or proton.
Several iron based LAILs with common cations are known Therefore, Brönsted acidic ionic liquid (BAIL) can be defined
and these ionic liquids are especially useful in catalysis as an ionic liquid substance that can donate a hydrogen ion
applications. These materials are a particularly attractive (H+) or proton. Those donating or easily releasable proton(s)
group due to moisture stability, magnetic liquid proper- in the BAIL can reside in a number of locations in the structure
ties,118−125 and the ability to form ionogels.126,127 Some of and can be further classified based on the location of the acidic
the noticeable catalysis applications include [C4C1im]Cl- proton(s). The most common locations you can find the acidic
1.5FeCl3 in glycosidation of 3,4,6-tri-O-acetyl-d-glucal with proton(s) are nitrogen or oxygen atoms, in the anion, and in
alcohols to give glycopyranosides,128 [C4C1im][FeCl4] in acidic functional groups (e.g., SO3H, CO2H) attached to the
Michael addition,129 polystyrene-supported Lewis acidic iron- cation. In addition to this BAILs can be classified based on the
containing ionic liquid for converting CO2 into cyclic synthesis method as well. The acidic ionic liquids are prepared
carbonate,130 [C4C1im][FeCl4] for benzylation of various by reacting a Brönsted base and a Brönsted acid. The BAILs
arenes/heteroarenes into the diarylmethanes,131 and glycol- with one or more acidic hydrogen(s) residing on N or O atoms
ysis.132 In addition [C4C1im][FeCl4] system has been used as a are known as protic ionic liquids (PILs) as well. In this review
desulfurizing agent133,134 and 1-ethyl-3-methylimidazolium protic ionic liquids with H+ in cations and anions will be
chloride ([C2C1im]Cl) with iron chlorides FeCl2 and FeCl3, referred to as a part of the larger collection of Brönsted acidic
for rechargeable batteries135 as well. Xia and Taubert have ionic liquids. Then the third group is acid group functionalized
reported another interesting property of FeCl4− anion ILs and in these compounds the acid group is generally
containing LAILs.136 In this instance, 1-butyl-3-methylimida- tethered to the cation. Therefore, BAILs can be further
zolium tetrachloroferrate(III) [C4C1im][FeCl4] and 1-dodecyl- classified into five different sub groups as shown below.
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 3.1. Protic Acidic Ionic Liquids with Acidic Hydrogens on
cation and substituting the halides (X) in the anion on their Cation
thermal behavior, IR, VU−vis spectra, density, viscosity, ionic The Brönsted acidic ionic liquids with acidic hydrogens residing
conductivity, and magnetic properties for a series of para- on the cationic side can be considered as a major group; this
magnetic ionic liquids.137 These LAILs were comprised of 1- sub group is commonly refered to as “protic ionic liquids” as
alkyl-3-methylimidazolium cation (R = Et, nBu, nhexyl and well. However, in this review the classification is further refined
n
octyl) and tetrahalogenoferrate(III) FeX4− anion (X = Cl and as protic acidic ionic liquids with acidic hydrogens on cation
Br). They found that the elongation of the alkyl chain leads to a and anion as two separate groups due to rapid growth in the
pronounced reduction of fluidity and ionic conductivity, and field. Greaves and Grummond have reviewed the literature on
6137 DOI: 10.1021/acs.chemrev.5b00763
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properties and applications of protic ionic liquids until 2008.139 plot.154−162 The Walden plot that makes allowance for
This type of ionic liquid is formed by stoichiometric reactions differences in ion sizes is shown to be an improvement to
between Brönsted acids and Brönsted bases. There are many this early approach, and in some cases it is feasible to directly
combinations of Brönsted acids and bases that can give stable quantify ionicity via the Nernst−Einstein equation, confirming
salts, but to obtain a true IL, it is necessary to have complete the validity of the adjusted Walden plot approach as well.163
(conventionally ∼99.9%) transfer of the proton from the acid NMR spectroscopy is another tool used in the study of
to the base. Generally, the aqueous pKa values of the precursor proton transfer in protic ionic liquids.164,150,153,165 In
acids and bases are regarded as predictive of the behavior of the imidazolium PILs the chemical shift of the protons attached
formed protic ILs; more accurately, ΔpKa values greater than to the nitrogen atom of imidazolium cation and imide anions
8−10 [ΔpKa = pKa(base) − pKa(acid)] are reported to were used by Watanabe’s group.153 In another example, Burrell
produce protic ILs of ideal ionicity.140 As far as we are aware, and co-workers studied 15N NMR spectra of a series of PAILs
the first ionic liquid was discovered by Gabriel in 1888, and this resulting from eight amine bases and six Brönsted acids.164 In
compound, ethanolammonium nitrate, is also a protic acidic this study it was possible to distinguish between neutral and
ionic liquid with acidic hydrogens on the cation.141,142 As ionized amine bases (ammonia vs ammonium-type ion), which
mentioned earlier this type of BAIL is synthesized by reacting indicated that the protic ionic liquids were completely ionized
equimolar amounts of Brönsted acids and Brönsted bases as when made as a stoichiometric mixture. However, a Walden
shown in Figure 4. 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
Figure 4. Synthesis of protic acidic ionic liquids with acidic hydrogens
on cation by proton transfer from Brönsted acid to Brönsted base.
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
Some selected examples of protic acidic ionic liquids with Anion
acidic hydrogens on cation are triethylammonium bromide,143 When the donating proton is located in the anion fragment of
bis(tetrafluoromethylsulfonyl)amide,144 pyridinium bromide,143 the acidic ionic liquid, these anions are generally derived from a
1-methylimidazolium chloride, bromide, iodide,143 BF4−, polybasic acid. The common acids used in PAILs are dibasic
CF3SO3−,145 1-butylimidazolium chloride,143 2-n‑butyl-1,1,3,3- sulfuric acid (H2SO4) and tribasic phosphoric acid (H3PO4);
tetramethylguanidinium acetate,146 pyrolidonium, and lactam replacement of all the hydrogens by ionic liquid cations forms
based BAILs.147 Some of these Brönsted acidic ionic liquids are neutral ionic liquids if there are no acidic hydrogens on the
shown in Figure 5. The tetramethylguanidinium compound is a cation. However, if all the hydrogens are not replaced in the
particularly interesting Brönsted acidic ionic liquid because it anions, PAILs with proton donor anions are formed.
act as a duel acid−base; H on N-2 acts as the Brönsted acid site, For example 1-butyl-3-methylimidazolium hydrogensulfate
whereas the N1 and N3 are tertiary amine groups with basic can be prepared by reacting 1-butyl-3-methylimidazolium
properties. chloride with one equivalent of sulfuric acid and removal of
In an ideal protic acidic ionic liquid synthesis, the Brönsted volatile HCl to drive the reaction to produce the protic acidic
acid and base react completely to produce the PAIL. However, ionic liquid as shown in Figure 6. In addition 1-butyl-3-methyl-
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 Figure 6. Synthesis of Brönsted acidic ionic liquids with proton donor
One of the widely used methods to measure ionicity for the anions.
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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Figure 7. Protic acidic ionic liquids with acidic hydrogens on anion.

imidazolium hydrogensulfate ionic liquid has been prepared by tethers are easily prepared using propyl or butylsultones as
using sodium bisulfate in place of concentrated sulfuric acid as shown in the first reaction in Figure 9. In the first step alkyl
well under microwave irradiation conditions with significantly imidazole reacts with sultone to give a zwitterionic salt, which
reduced reaction times.167 can be treated with a Brönsted acid like HCl or HBr to give the
Some selected examples for protic acidic ionic liquids with desired BAIL.175,176,173 Another method that has attracted
acidic hydrogens on the anion are dialkylimidazolium hydro-
recent attention is the sulfonation of an aromatic system in the
gensulfate,168−171 dialkylimidazolium dihydrogen phosphate,170
and maleic and fumaric acid anions derived PAILs. A selected neutral ionic liquid as shown in the second reaction in Figure
sample of this type of Brönsted acidic ionic liquids is shown in 9.177 The carboxylic acid functionalized acidic ionic liquids are
Figure 7. generally synthesized via the corresponding carboxylic acid
3.3. Protic Acidic Ionic Liquids with Acidic Hydrogens on esters.178
Cation and Anion A wide variation in ionic core structures and multiple acidic
There are protic ionic liquids with H+ on the cation as well as group containing BAILs are known, and some common
on the anion such as diethylmethylammonium hydrogensulfate examples are shown in Figure 10.
[(C2)2C1HN][HSO4] described by Watanabe and co-workers 3.5. Brö nsted Acidic Ionic Liquids with Acidic Hydrogens
for prospective use as a fuel cell electrolyte.172 These are easier on Functional Groups and on an Anion or Cation
to prepare by partial neutralization of a polybasic acid with an The fifth type of BAILs can have two or more H+ on the acidic
organic base and some common examples are shown in Figure
functional groups and on the anion or cation. There are a
8.
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
Figure 8. Protic ionic liquids with acidic hydrogens on cation and using sultones.179 Meng and co-workers has extended this
anion. technique to produce a series of BAILs with multiple H+ on
−SO3H and nitrogens.179 The third reaction is the synthesis of
3.4. Brönsted Acidic Ionic Liquids with Acidic Hydrogens a caffeine based Brönsted acidic ionic liquid with a −SO3H
on a Functional Group group and an acidic anion.180 The anion exchange with
The fourth group of Brönsted acidic ionic liquids is the AILs polybasic acids such as H2SO4 and H3PO4 is also a valuable
with an acidic functional group tethered to the ionic core technique in introducing acidic anions in these BAILs.181,182
structure. This group can be seen as a type of functionalized A selected sample of Brönsted acidic ionic liquids with H+ on
ionic liquid as well. Forbes, Davis, and others first described the acidic functional groups and on the anion or cation is shown in
preparation of this type of strongly acidic BAILS with a −SO3H Figure 12. Butylsulfonic-1,1,3,3-tetramethylguanidinium triflate
group tethered to an ionic group in 2002.173 Nevertheless, The is an example of a BAIL with an acidic functional group and H+
synthetic approach used to assemble the zwitterionic precursors on the cation.183 In addition acidic ionic liquids with several
to these acidic IL was reported by Yoshizawa et al. 2001.174 acidic H+ on multiple locations are also known. For example,
They synthesized a series of imidazolium cations containing N,N′,N″,N‴-tetrapropyl sulfonic hexamethylenetetramine tetra-
covalently bound anionic sites, such as sulfonate or sulfonamide
hydrosulfate is a BAIL with eight acidic hydrogens.184 The
groups. These zwitterionic imidazolium salts were found to
form molten salts just like ordinary imidazolium salts. The acid acidic ionic liquid (4-butylsulfonic)tris(4-phenylsulfonic)-
group can be attached to the ionic core directly or via a carbon phosphonium hydrogensulfate is another example. This highly
chain or a ring system. There are several methods of making decorated molecule was described as a catalyst by Shaterian and
this type of BAILs. One widely used approach is the sultone co-workers and is an example of a BAIL with three different
method; by which −SO3H functionalized ILs with C3 and C4 types of acidic protons.185

Figure 9. Two methods of preparation of −SO3H functionalized BAILs.

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Figure 10. Brönsted acidic ionic liquids with acidic hydrogen containing functional groups attached to the cation.

[(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.


Figure 11. Synthesis of Brönsted acidic ionic liquids with acidic
hydrogens on functional group as well as on cation/anion.177
Al, Zn, and Fe are the common Lewis acids used in
Brö nsted−Lewis acidic ionic liquids.194 However, Cu(1)
4. BRÖ NSTED-LEWIS ACIDIC IONIC LIQUIDS containing ionic liquids were also reported recently,195 where
The group of acidic ionic liquids with both Brönsted and Lewis a series of Brönsted−Lewis acidic Ionic liquids were prepared
acidic characteristics in the same molecule is known as duel- by changing the Cu to BAIL mole ratio. In this method
functionalized ionic liquids as well and is a relatively smaller [(HSO3)3C3C1im][HSO4] and CuO were mixed in distilled
class. This type of AILs is particularly useful as catalysts as some water in the desired ratio, the solution was then stirred
catalytic processes require both types of acidities in one or continuously for about 2 h at 308 K and dried in vacuum to
more steps of the reaction. Synthesis and applications of produce a series of ILs with formulas such as
Brönsted-Lewis acidic ionic liquids have been reviewed in a [(HSO3)3C3C1im][(1/2Cu2+)SO42−] and [(HSO3)3C3C1im]-
short review of 37 references in 2012.186 [(1/2H+.1/4Cu2+)SO42−].195 These task specific Brönsted−
Examples for Brönsted−Lewis acidic ionic liquids of N- Lewis acidic ionic liquids are known in various applications
methylpyrrolidonium zinc chloride [C1HPyrr][ZnCl3],187 including catalysis196−198 and desulfurization of diesel fuel.187

Figure 12. Brönsted acidic ionic liquids with acidic hydrogens on functional groups as well as on cation/anion.

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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 Figure 15. Synthesis of a polymeric acidic ionic liquid with acidic ionic
AIL.189 liquid as pendent groups.211

5. POLYMERIC ACIDIC IONIC LIQUIDS


conductive films.223 In this approach ionic liquid crystals with
Polymeric acidic ionic liquids are an emerging subgroup in hexagonal and lamellar phases were successfully fabricated by
AILs, which can combine all three: acidic, ionic liquid and self-assembly based on intermolecular electrostatic interactions.
polymer properties to a single material. The swift progress and The polymerizable amphiphilic zwitterions are formed by the
explosive growth in polymeric ionic liquids area is reflected by reaction of 3-(1-vinyl-3-imidazolio)propanesulfonate (VIPS)
the large body of recent publications and some recent with 4-dodecyl benzenesulfonic acid (DBSA).223
reviews199−205 and particularly the imidazolium-based poly-
meric acidic ionic liquids are discussed in two recent dedicated 6. IMMOBILIZED ACIDIC IONIC LIQUIDS
reviews206,207 justifying the importance of these polymers.
Polymeric acidic ionic liquids with ionic liquid and acid groups Immobilization of acidic ionic liquids can be carried out on
as pendant group in a polymer chain are the most common soluble or insoluble supports. However, the most common
type. There are two basic synthetic approaches for assembling examples are in the area of using insoluble supports to produce
this type of materials. These two methods are grafting the acidic heterogeneous acid catalyst systems. In many cases these
ionic liquid groups on to an existing polymer and polymer- heterogeneous catalysts showed enhanced size and positional
ization of an ionic liquid or AIL precursor. selectivity compared to homogeneous catalysts as the solid
support imposes a specially designed environment around the
5.1. Acidic Ionic Liquid Groups Grafted onto an Existing catalytic site.75 In addition, the immobilization may prevent
Polymer molecular aggregation or bimolecular self-destruction reactions,
A handful of examples of this type is known, which includes; which leads to deactivation of the catalytic sites. The most
immobilization of imidazolium - HSO4 on to a polymeric important advantage is the ease of separation of the supported
support based on calix[4]resorcinarene,208 carboxyl function- acidic ionic liquid from reactants and products for reuse. The
alized dication imidazolium-based ionic liquids209 and immobi- commonly used supports are silica, alumina, zeolites and
lization of pyridinium propanesulfonic acid catalyst on polystyrene type polymers. A 2014 review titled “The use of
polychlorostyrene spheres.210 supported acidic ionic liquids in organic synthesis” with 79
5.2. Polymerization of an Acidic Ionic Liquid Monomer references summarizes the recent progress in both inorganic
Polymerization of an acidic ionic liquid monomer or a and organic supported AILs in catalysis applications.75
precursor is a more widely investigated approach. The general 6.1. Immobilized on Inorganic Supports
examples include: imidazolium −SO3H heteropolyanion,211−215 Silica is the most widely used, convenient, and acid stable solid
poly(4-vinylpyridine),216−219 copolymerization of acidic ionic support for BAILs, although there are a few examples in use of
liquid oligomers and divinylbenzene (DVB),220 polymerization zeolites and metal organic frameworks as well.224 There are
of 2-acrylamido-2-methyl-1-propanesulfonic acid salt of butyl- three basic techniques of immobilization, which involve grafting
amine,221 and resorcinol-formaldehyde222 based polymeric of catalyst on to a silica surface, synthesis of silica material by
acidic ionic liquids. Some of the common examples are sol−gel formation, and adsorption on the solid surface. In 2010,
shown in Figure 14. 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
Figure 14. Some common polymeric acidic ionic liquids prepared by al. grafted the BAIL group on to 3-mercaptopropyltrimethox-
polymerization of an acidic ionic liquid monomer. ysilane modified silica gel by a free radical coupling reaction and
this catalyst was used for the esterification and nitration of
In one example, Leng and co-workers reported the synthesis aromatic compounds.226 Similar BAIL catalysts have been used
of a −SO3H functionalized heteropolyanion containing in the esterification of oleic acid,227 synthesis of bis(indolyl)-
polymeric acidic ionic liquid by polymerization of the methanes,228 conjugate addition of indoles,229 and thioacetal-
zwitterionic monomer as shown in Figure 15.211 In addition ization of carbonyl compounds in water.230
they used the new polymer as a heterogeneous catalyst for an Another common technique of immobilization of a catalyst
esterification reaction.211 on silica is sol−gel synthesis by hydrolysis of a mixture of
The photopolymerization of acidic ionic liquid components silicates like tetraethyl orthosilicate (TEOS), and a silicate with
has been used in the fabrication of nanostructured proton- covalently linked catalytic function. This method has been
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Figure 16. Synthesis of sulfonic acid functionalized acidic ionic liquid modified silica catalysts by grafting method.

successfully applied for the immobilization of acidic ionic ILs were calculated by using the van’t Hoff equation. This study
liquids. For example Miao and co-workers immobilized 1-(3- provides some useful information for further research and
propylsulfonic) imidazolium hydrogensulfate on silica−gel applications of AILs.303
using tetraethyl orthosilicate as the primary silica source as In 2014 the physical propertiesdensity, viscosity, molecular
shown in Figure 17.231 Selected examples of immobilizations of volume, standard entropy, thermal expansion coefficient, and
AILs on inorganic supports and catalytic applications of the crystal energyof four common Brönsted acidic ILs, 1-(3-
immobilized AILs are shown in Table 2. 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
Figure 17. Synthesis of sulfonic acid functionalized acidic ionic liquid viscosity of these ILs are shown in Table 4, whereas molecular
modified silica catalyst by sol−gel synthesis method.231 volume Vm, standard entropy S0, thermal expansion coefficient
(αp) and crystal energy UPOT are shown in Table 5.
Immobilization by adsorption or entrapment in an inorganic Standard entropy S0 was calculated using the equation
support is another approach of immobilization of a catalyst, S 0 = 1246.5(Vm) + 29.5
which has been applied to AILs as well.281 Marr and co-workers
prepared a catalyst with (3-propylsulfonic)-trimethylammo- where Vm is the molecular volume in nm3 and S0 is the standard
nium type ionic liquid [(HSO3)3C3(C2)3N] ][NTf2] entrapped entropy in J K−1 mol−1. Lattice energy (UPOT) is reflected by
within silica gel. This silica gel containing functionalized acidic the strength of the interactions between its ions. This was
ionic liquid was used as a recyclable liquid phase catalyst for the calculated using the following equation based on the Glasser
dehydration of rac-1-phenyl ethanol. Furthermore, hot filtration theory.305
tests showed that the activity was within the gel.281
UPOT = 1981.2(ρ /M) + 103.8
6.2. Immobilized on Organic Supports
Acidic ionic liquid immobilized on organic polymeric structures The thermal expansion coefficient (αp) values were
are also known. Polystyrene immobilized acidic ionic liquids are calculated using the equation304 αp = −A1/(A0 + A1T) where
generally prepared by copolymerization of a mixture of a BAIL A0 and A1 are the fitting parameters that have been determined
attached vinylbenzene and divinylbenzene as shown in Figure from the plot between density and temperature, while T is the
18.282 absolute temperature. The thermal expansion coefficient values
The polystyrene based systems are the most widely used reflected the free volume of ionic liquid; that is, higher thermal
organic supports, in addition poly(vinylpyridine)216 and coefficient values correspond to higher free volume of ionic
melamine resins283 have also been used as solid supports for liquid, similar to other types of imidazolium-based ILs.306,307 It
AILs. The recent examples of immobilization on organic is interesting to note that relatively low values of thermal
supports are listed in Table 3. expansion coefficients were obtained for these ILs, and this
could be due to more compact spatial molecular structures of
7. PHYSICAL PROPERTIES OF ACIDIC IONIC LIQUIDS the ILs.
Viscosity and particularly the temperature dependence of the
7.1. Solubility, Density, Viscosity, and Related Properties viscosity or rheology properties of protic ionic liquids is an area
Interest in physical properties of AILs has seen a rapid growth of particular interest as these measurements provides
as the applications have widened in the last 5−6 years. Wang information regarding H-bonding network in the
and co-workers studied the solubilities of benzothiazolium PAILs.308−311 Atkin and co-workers studied the rheological
acidic ionic liquids in common alcohols (methanol, ethanol, 1- properties of a series of protic ionic liquids, ethylammonium
propanol, 2-propanol, 1-butanol, and 2-methyl-1-propanol) at nitrate [C 2 (H) 2 N][NO 3 ], propylammonium nitrate
temperatures 253−384 K using a static equilibrium method [C3(H)2N][NO3], ethanol ammonium nitrate [HO2C2(H)2N]-
under atmospheric pressure.303 The modified Apelblat equation [NO3], ethylammonium formate [C2(H)2N][HCO2], and
and λh equation were employed to correlate the experimental dimethylethylammonium formate [C2(C1) 2H3N][HCO2].
data with good agreement. It was interesting to find that the They interpreted the viscosity data by considering the effects
solubilities of some ILs in alcohols were with “temperature- of both the H-bond network and the solvophobic nanostruc-
sensitive” properties. The solubility is related to the polarity and ture of the liquids.309 At 20 °C, [C2(H)2N][NO3] has the
molecular structures of the solvent, as well as the strength of highest zero shear viscosity of 156.1 mPa s, followed by
hydrogen bonding between alcohols and anionic groups of ILs. [C3(H)2N][NO3]. They found that primary ammonium ILs
During these studies the dissolution enthalpy and entropy of 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

6143
hydrogen sulfate - Pt
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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Chemical Reviews Review

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
6145 DOI: 10.1021/acs.chemrev.5b00763
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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 Review

([1C1Him][NTf2], [1C2Him][NTf2], and [1C12C1Him][NTf2]) Table 8. Selected Set of References for Spectroscopy of
have an acidic N−H group in the imidazolium ring, which is in Common Acidic Ionic Liquids
agreement with the observed increase in energy barrier of flow. acidic ionic liquid type spectroscopy refs
The methylation in C-2 position as well as the N−H acidic 1-(alkyl sulfonic)-3-alkylimidazolium and IR, 1H, 13C 344−350
group in the imidazolium ring contributes to a significant imidazolium PAILs NMR, mass
variation in the cation−anion interactions and their dynamics, pyridinium hydrogensulfate IR, 1H, 13C 351−353
NMR
which is reflected in their charge distribution and polarizability
alkyl sulfonic acid benzimidazolium IR, 1H, 13C 354
leading to a significant differentiation of the refractive indices, NMR
surface tension, and heat capacities.333 1,1′-disulfo-[2,2′-bipyridine]-1,1′-diium IR, 1H, 13C 355
chloride NMR
7.4. Ionic Conductivity succinimidinium N-sulfonic acid IR, 1H, 13C 356,357
NMR
Ionic conductivity of AILs in relation to structure is another 1
alkylsulfonic ammonium, [(C2)2H2N][OTf] H, 13C NMR 358−362
useful tool in extracting structural information.334−336 The self- and [(C2)3HN][OAc]
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 8. COMPUTATIONAL STUDIES ON ACIDIC IONIC
common approach applicable in protic ionic liquids.338 In a LIQUIDS
recent investigation Wu and co-workers studied the ionic 8.1. Computational Studies on Acidity and Other Physical
conductivities of a series of protic ionic liquids based on Properties
acetamide and Brönsted acids (HX, where X is CF3COO−, Several research groups have used computational methods to
CH 3 COO −, or HSO 4 − ). They found that the ionic predict and explain acidity related parameters, hydrogen
conductivities for most of the samples are between 10−3 and bonding characteristics and molecular geometries of Lewis
10−1 S/m at room temperature. Acetamide trifluoroacetate with and Brönsted acidic ionic liquids.376−378 Liu and co-workers
acetamide: trifluoroacetic acid 1:1 mol ratio showed an ionic used density functional theory to study the −SO3H function-
alized acidic ionic liquid 1-(3-propylsulfonic)-3-methylimidazo-
conductivity of 0.25 S/m, and a viscosity of 10 cP at 25 °C. lium hydrogen sulfate [(HSO3)3C3C1im][HSO4] and its
Moreover, most of the AILs studied possessed relatively precursor zwitterion compound.379 These species were
moderate thermal stabilities (up to 106 °C for acetamide optimized systematically by the DFT theory at B3LYP/6-
trifluoroacetate) and a wide liquid range (down to −69 °C for 311++G** level, and their most stable geometries were
acetamide trifluoroacetate). The ionic conductivity properties obtained. The calculation results indicated a great tendency
observed in this study may perhaps make these acetamide- to form strong intramolecular hydrogen bonds in the
based PILs of interest as reaction media, catalysts in organic zwitterion, and this tendency was weakened in the cation,
synthesis, or as electrolytes in fuel cells.334 which was the protonation product of the zwitterion. The
intramolecular hydrogen bonds and intermolecular hydrogen
7.5. Spectroscopy bonds coexisted in the ionic liquid, and they played an
The NMR characterizations of acidic ionic liquids are reported important role in the stability of the systems. The strongest
in some publications on synthesis and applications of AILs and interaction in the ionic liquid was found between the anion and
the functional group. The transition state research and the
in most cases the NMR spectra are recorded in D2O or DMSO-
intrinsic reaction coordinate analysis of the hydrogen transfer
d6. In addition to the structural characterization, NMR reaction showed that when the cation and the anion interacted
spectroscopy have been used in the determination of acidity near the functional group by double O−H···O hydrogen bonds,
in ionic liquids,315,339 study AILs in aqueous environments,340 the ionic liquid was inclined to exist in a form of the zwitterion
ion-pairing behavior,341 anion speciation by 119Sn342 and 27Al343 and H2SO4.379 In addition the acidity in imidazolium
NMR spectroscopy. For instance Lewis and Brönsted acidic bromoalumanate LAILs have also been examined using DFT
species of chloroaluminate ILs have been investigated by 27Al methods.376
NMR spectroscopy. These experiments revealed that Lewis In a recent study dynamic simulation based on the ion pair
acidity arises mainly from Al2Cl7−, having a chemical shift at charge approach has been performed to investigate the
structural characteristic of −SO3H functionalized ILs in the
102 ppm in the 27Al NMR spectrum, while Brönsted acidity development of new proton conductive materials.380 In this
arises from Al2Cl6OH− (chem. shift at 97 ppm). The peak at 94 study Shan and co-workers found that there are significant
ppm in the 27Al NMR spectrum is related to Al2Cl5O−.339 A aggregations of sulfonic acid side chains due to strong
selected set of references for UV−vis, IR, and 1H and 13C interactions between different sulfonic acid groups. Further-
NMR, mass spectroscopy of common acidic ionic liquids are more, they observed that after the introduction of a sulfonic
shown in Table 8. acid group to the side chain of the cation, the properties of the
anions have a remarkable influence on the preferential location
7.6. Miscellaneous Physical Properties
of anions in the interfacial region.380
In addition to the physical properties discussed, a number of 8.2. Computational Studies on Acidic Ionic liquid Catalysis
other interesting characteristics of AILs have been explored in There are a handful of cases where computational methods
recent years. These include studies on aggregation, crystal have been used for explaining the mechanisms, product
structure, chiral recognition and some of these examples are distributions, and stabilities by computational methods in AIL
shown in Table 9. 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) physicochemical properties studied refs
amines neutralized by bis(trifluoromethanesulfonic) amide, Alkanol amines neutralized by organic temperature dependencies of density, viscosity, 363−366
acids, 1,8-diazabicyclo[5,4,0]undec-7-ene neutralized by Brönsted acids and [(C4)3HP][BF4] conductivity, and electrochemical activity
decahydroisoquinoline neutralized by Brönsted acids ionicity and fragility 159
heterocyclic amines neutralized by trifluoroacetic acid capacitance with a RuO2 electrode and energy 367
storage mechanisms
[Pyrr][HSO4] and [Pyrr][OTf] self-diffusion coefficients and conductivities 336
[(HO2C2)H3N][C4−COO] aggregation by 1H, and 13C NMR spectroscopy 368
ephedrines neutralized by bis(trifluoromethanesulfonyl)amide and bis(pentafluoroethanesulfonyl) chiral recognition 369
amide
[(HO2C2)H3N][oleate] effect of temperature on density, speed of 370
sound, viscosity, and refractive index
[Hbim][Tfsa] (Tfsa= bis(trifluoromethanesulfonyl)amide) proton conductivity by Raman and NMR 371
spectroscopy
N-(2-hydroxyethyl)piperazinium propionate molar volume, viscosity and electrical 372
conductivity
[(HO2C2)H3N][NO3] thermal conductivity 373
[C2Him][OTf] ion−ion association by molar conductivity 374
1-ethyl-2-butyl-benzimidazolium tetra-fluoroborate crystallographic structure by X-ray diffraction 375
analysis

imidazolium cation [C2C1im]+ and chloroaluminate (AlCl4 − cases the specific acid is the protonated form of the solvent in
and Al2Cl7 −) catalyzed Diels−Alder cyclo-addition of methyl which the reaction is being performed. General acid catalysis is
acrylate to cyclopentadiene,381 removal of dibenzothiophene a system in which more than one species behaves as an acid.
and 4,6-dimethyldibenzothiophene from model diesel,382 Acidic ionic liquids are used in applications where they behave
glucose transformations, 383 extractive desulfurization in as Lewis and Brönsted acids as well as in reactions involving
[C4C1im][AlCl4],384 ether formation,385 and biodiesel syn- both mechanisms. In addition AILs are known in the form of
thesis.386 In a recent development Li and co-workers reported a homogeneous and heterogeneous acid catalysts as well. In
DFT study on the mechanism for 1-(4-butylsulfonic)-3- numerous cases the substitution of a conventional acid with an
methylimidazolium hydrogen sulfate [(HSO3) 4C 4C 1im]- AIL has resulted in improvements in yield, turnover number
[HSO4] catalyzed conversion of glucose into 5-hydroxyme- (TON), or turnover frequencies (TOF) and catalyst
thylfurfural. They found that the conversion may proceed via recyclabilities, outperforming their traditional counterparts
two potential pathways and that throughout most elementary when used in classical reactions.
steps; the cation of BAIL plays a substantial role, functioning as 9.1.1. Esterification and Saponification. Esterification
a proton shuttle to promote the reaction. The chloride anion and saponification are industrially important and widely studied
interacts with the substrate and the acidic proton in the acid catalyzed reactions. A fair number of researchers have
imidazolium ring via H-bond, as well as provides a polar studied the possibility of substitution of classical acid catalysts
environment together with the imidazolium cation to stabilize with AILs for these reactions.389 The biodiesel synthesis is in
intermediates and transition states. The calculated overall fact a good example of saponification-esterification process;
barriers of the catalytic conversion along two potential however, biodiesel synthesis is presented as a separate subtopic
pathways are 32.9 and 31.0 kcal/mol respectively, which are in this review as it is an extensively studied current application
compatible with the observed catalytic performance of the AIL that needs special attention. Therefore, only esterifications and
under mild conditions (100 °C).387 The fixation of carbon saponifications which are not directly related to biodiesel
dioxide with epoxides catalyzed by a carboxylic acid function- production are covered in this section. Only about a dozen
alized IL catalyst has also been investigated using computa- examples are known in homogeneous catalysis area, however
tional methods. In this case, catalysis mechanism of 1-(2- some trans-esterification390,391 and considerable variations in
carboxyethyl)pyridinium-4-carboxylic acid bromide was ex- acidic ionic liquid types are known. For instance hydrophobic
plored using density functional theory techniques.388 1-(4-butylsulfonic)-3-octylimidazolium hydrogen sulfate
[(HSO3)4C4C8im][HSO4] has been used as an efficient catalyst
9. APPLICATIONS OF ACIDIC IONIC LIQUIDS for esterification of oleic acid with methanol392 with excellent
results, and some selected examples from recent applications
9.1. Catalysis Applications are shown in Table 10. In addition to the homogeneous acid
In acid catalysis there are typical Lewis acid catalyzed reactions catalysis, AILs have been used as supported heterogeneous
like Friedel−Crafts alkylation and Brönsted acid catalyzed catalysts as well in esterification. In one example, a series of
reactions like esterification. Lewis acid catalyzed reactions are polystyrene-supported 1-(3-propylsulfonic)-3-methylimidazo-
noticeable by electron transfer toward electron deficient Lewis lium hydrogensulfate catalysts with different acidic ionic liquid
acid and formation of a charge separated complex. Brönsted contents have been tested for esterification of n‑butyl alcohol
acid catalyzed reactions are marked by proton transfer, and in with acetic acid. In this study, the reactivity of the catalyst
these reactions proton transfer can make one reacting partner increased with increasing [(HSO3)3C3C1im][HSO4] content,
more electrophilic. Then acid catalysis can occur in two and a 98% yield of n‑butyl acetate was obtained with the best
different ways: specific acid catalysis and general acid catalysis. catalyst.292
Specific-acid catalysis refers to a process in which the reaction 9.1.2. Alkylation. Alkylation or the attachment of an alkyl
rate depends upon the specific acid in the solution. In most 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 The Friedel−Crafts type alkylation at a carbon atom is the
generally an electrophilic alkylation. One common example is most common application in acidic ionic liquid catalyzed
the Friedel−Crafts type alkylation, in which a Lewis acid alkylations.420−424 However, there are examples of alkylations at
catalyst is used to generate the carbocation, which acts as the N, O and S atoms as well.425,426 Acidic ionic liquid catalyzed
electrophile in the reaction. Lewis and Brönsted acidic ionic alkylation of phenol and phenol derivatives like cresols are well-
liquids can be used to generate carbocations and the acidic known.427 Alkenes or tertiary alcohols such as t‑butanol are
ionic liquids are often more effective than common Lewis and common alkylating agents used in this reaction. For example,
mineral acids in these reactions. In 2013 Zhang et al. reviewed Elavarasan and co-workers tested catalytic activities of three
the application of acidic ionic liquids as a catalyst in the BAILs in the t‑butylation of phenol with t‑butyl alcohol (TBA)
alkylation reaction.418 The methods used in the determination as shown in Figure 21.428 The reaction time, temperature, and
of acidity, application of acidic ionic liquids in alkylation, acidic reactant/catalyst mole ratio were optimized in this study.
adjustment methods, and novel acidic ionic liquids are Among the three ionic liquids studied, triethylammonium based
discussed in this review article with 38 references.418 Earlier sulfonic acid functionalized ionic liquid was found to be the
Qiao wrote a review on benzene alkylation with long chain most promising and gave the highest phenol conversion. A
olefins catalyzed by ionic liquids as well, and this review is comparison of catalyst performances in the alkylation of phenol
particularly focused on the applications of chloroaluminate with t‑butyl alcohol is shown in Table 11. Additionally they
ionic liquids in benzene alkylation of special interest to found that the catalyst retained its activity even after 5 recycles.
petrochemical and detergent industry.419 The activation energy for ionic liquid catalyzed alkylation of
6149 DOI: 10.1021/acs.chemrev.5b00763
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Chemical Reviews Review

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 As described earlier there are numerous applications of acidic
ionic liquids in alkylation reactions and some selected examples
better than those obtained with the commercial H2SO4 catalyst and their references are shown in Table 13.
9.1.3. Acetalization. Acetalization is another acid catalyzed
(65% TMP selectivity, 97 RON) and pure triflic acid.442 reaction tested with BAILs, where (4-butylsulfonic)-triethy-
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lammonium hydrogensulfate [(HSO3)4C4(C2)3N][HSO4] was Brönsted acidic ionic liquids to generate the carbonium ions
reported to give excellent yields in the production of fructone and subsequent reactions in the ionic liquid media is known in
via the acetalization reaction of ethyl acetoacetate with ethylene named reactions like the pinacol rearrangement173 and Ritter
glycol.325,493 The condensation of glycerol, a platform chemical reaction558 as well as in isomerizations.559 Kalkhambkar558 and
from renewable materials with benzaldehyde to generate cyclic co-workers have used imidazolium ionic liquid 1-(4-butylsul-
acetals has been investigated using BAIL catalysts. Evidence was fonic)-3-methylimidazolium triflate [(HSO3)4C4 C1im][OTf]
presented for the formation of a product mixture with 4- as catalyst for the high yield synthesis of a wide variety of
hydroxymethyl-2-phenyl-1,3-dioxolane and 5-hydroxyl-2-phe- amides under mild conditions via the Ritter reaction of alcohols
nyl-1,3-dioxane as cis and trans stereoisomers. Under optimum with nitriles as shown in Figure 25.
reaction conditions butyl-pyridinium hydrogensulfate [C4pyr]- In another recent work efficient and selective rearrangements
[HSO4] catalyst produced a 99.8% yield of acetals at room of stilbene epoxides were observed with 0.1−0.3 equiv of
temperature.494 [(HSO3)4C4C1im][OTf] in dichloromethane as shown in
9.1.4. Heterocyclic Synthesis. The use of Brönsted acidic Figure 26. A substituent effect study was performed with a
ionic liquids in heterocyclic synthesis is a well documented series of singly substituted 1,2-diphenyl oxiranes and competing
application. A fair number of classical heterocyclic syntheses formation of ketones was observed in acidic ionic liquids.560
done with Lewis and Brönsted acids have been tested with In another application propargylic alcohols were converted to
BAILs and in many cases BAILs have proven to be better cyclic and acyclic α,β-unsaturated enones using
catalysts than equivalent dose of traditional acids. Some of the [(HSO3)4C4C1im][OTf] as the catalyst and [C4C1im][PF6]
initial applications are discussed in a few earlier ionic liquid as the solvent via the Rupe rearrangement as shown in the
review articles495−498 and in a book titled “Ionic Liquids in example in Figure 27.561
Synthesis”.499 The 2008 review titled “Ionic Liquids in Pinacol rearrangement of hydrobenzoin using triethylammo-
Heterocyclic Synthesis” with 367 references gives a compre- nium hydrogensulfate [(C2)3NH][HSO4] as the catalyst is
hensive account on the use of neutral, acidic and basic ILs as another example for carbonium ion generation and rearrange-
solvents and catalysts in the synthesis of many classes of ment as shown in Figure 28.562 The optimal conditions were
heterocyclic compounds.500 found to be heating at 80 °C for 5 min under low power
In a recent application, 1-(3-propylsulfonic)-3-methylimida- microwave (20 W) conditions to avoid ionic liquid degradation.
zolium chloride [(HSO3)3C3C1im][Cl] and 1-(4-butylsul- Lewis acidic ionic liquids like pyridinium chloroaluminate has
fonic)-3-methylimidazolium chloride [(HSO3)4C4C1im][Cl] been used in isomerization of exo-tetrahydrodicyclopentadiene
BAILs are shown as excellent catalysts and reaction mediums to adamantane.563,564 Rearrangements of terpenes is another
for Skraup synthesis of quinolines under microwave con- area of interest, where 1-(3-propylsulfonic)-3-methylimidazo-
ditions501 (Figure 24). There are a number of advantages to 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
Figure 24. 1-(Alkylsulfonic)-3-methylimidazolium chloride Brönsted resources based route to this C3 aldehyde; liquid phase170 as
acidic ionic liquid catalyzed Skraup synthesis of quinolines under well as solid supported acidic ionic liquid catalyzed methods are
microwave heating. reported to this important feedstock in the recent liter-
ature.567,568 Shen and co-workers have investigated a liquid
using the BAILs as reaction mediums and catalysts in the phase dehydration of glycerol to acrolein catalyzed by BAIL
Skraup synthesis. These include: shorter reaction time, better using the semibatch reaction technique. They found that for a
yields, ease of isolation of the quinoline product, and most series of BAIL catalysts, the acrolein yields were in the order of
importantly elimination of the use nitrobenzene or other [C4C1im][H2PO4] > [C4C1im][HSO4] > [C4Py][HSO4] >
oxidizing agents and additional metal catalysts.501 [(HSO3)3C3Py][HSO4] > [C4(C2)3N][HSO4] >
The BAILs on solid supports have been used in heterocyclic [(HSO3)3C3Py][H2PO4] > [C4Py][H2PO4] > [C4(C2)3N]-
synthesis.502 In this application, Fe2O3-MCM-41 materials with [H2PO4]. When [C4C1im][H2PO4] and [C4C1im][HSO4]
1-(4-butylsulfonic)-3-propylimidazolium hydrogensulfate has were used as the catalysts at 270 °C with the molar ratio of
been used as the catalyst for the one-pot synthesis of catalyst to glycerol of 1:100, the acrolein yields were 57.4% and
pyrimido[4,5-d]pyrimidine derivatives as well as 2-amino-4H- 50.8%, respectively, at complete conversion of glycerol.170
chromenes503 using 6-aminouracil, aldehydes, and urea or Nevertheless in the dehydration of ethanol to ethylene, Gong et
thiourea under solvent free conditions.504 Some selected al. found that the catalytic activity of 1-(4-butylsulfonic)-3-
examples of heterocyclic synthesis using acidic ionic liquids as methylimidazolium hydrogen sulfate [(HSO 3) 4C4 C1 im]-
catalysts are shown in Table 14. [HSO4] is similar to H2SO4.569
9.1.5. Carbonium Ion Generation and Rearrange- 9.1.7. Oxidation. In another application BAIL catalysts
ments. Acidic ionic liquid catalyzed carbonium ion generation have been used in the oxidation of alcohols to aldehydes and
and rearrangements of the resulting carbonium ions is another ketones. In this instance, −SO3H functionalized heteropolyan-
reaction receiving attention. In many examples the carbonium ion-based ionic liquids with 35% aqueous H2O2 were used
ion rearrangement product distributions are influenced by the without adding any phase transfer catalyst as shown in Figure
AIL catalysts as compared with traditional acids. The use of 29.570 For the aliphatic alcohols corresponding aldehydes and
6152 DOI: 10.1021/acs.chemrev.5b00763
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Chemical Reviews Review

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) reaction refs
3-sulfonic-1-imidazolopyridinium hydrogensulfate 2H-indazolo[2,1-b]phthalazine-1,6,11(13H)-triones 180
[(HSO3)4C4(2-HSO3−Ph)3P][HSO4] 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
Figure 25. [(HSO3)4C4C1im][OTf] catalyzed Ritter reaction558
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
Figure 26. [(HSO3)4C4 C1im][OTf] catalyzed rearrangements of polyaspartic acid under microwave irradiation.573 Tian et al.
stilbene epoxides560 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
Figure 27. [(HSO3)4C4C1im][OTf] catalyzed rearrangement of a
acetylation. Fully substituted cellulose acetate with a conversion
propargylic alcohol to α,β−unsaturated enone via the Rupe rearrange-
ment.561 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
Figure 28. Pinacol rearrangement of hydrobenzoin under microwave hydrogen sulfate [C6C1im][HSO4],579 and degradation of
irradiation using [(C2)3NH][HSO4] catalyst562 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
Figure 29. Oxidation of alcohols with H2O2 catalyzed by long chain epichlorohydrin as an intermediate product, and utilizes HCl
−SO3H functionalized heteropolyanion-based ionic liquids under as a recycling agent. Among various BAIL catalysts investigated,
solvent-free conditions.570
the acidic ionic liquid (4-butylsulfonic)-trimethylammonium
hydrogensulfate [(HSO3)4C4(C1)3N][HSO4] exhibited the
ketones were obtained in 63%−100% yields using SiW12O404− highest activity and selectivity in the process.586 N-Boc
anions. For benzyl alcohols, the corresponding benzoic acids protection of amines is a common synthetic operation. Shirini
were obtained in 64%−94% yields using PW12O403− anions. and co-workers have introduced a new class of BAIL,

Table 15. Application of Acidic Ionic Liquids in Polymerization and Oligomerization Reactions

acidic ionic liquid catalyst(s) polymerization/oligomerization reaction refs


[C4C1im][AlCl4] and [(EtOCOCH2)C1im][AlCl4] α-pinene polymerization 581,582
[(HSO3)4C4 C1im][OTf], [(HSO3)4C4 C1im][BF4], [(HSO3)4C4 C1im][OTs], [(HSO3)4C4 C1im][HSO4], copolymerization of lactic acid and ε- 583
[(HSO3)4C4 Py][ HSO4] and caprolactone
[(HSO3)4C4 (alkyl)im][HSO4] supported on silica gel oligomerization of isobutene 265
[HPyrr][HSO4] homo and graft polymerization of ε- 584
caprolactone
Multi-SO3H-functionalized ionic liquid polymerization of lactic acid-ethylene 585
glycol

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succinimidinium hydrogensulfate, as efficient catalysts for the 9.2.1. Cyclic Carbonate Synthesis. Cyclic carbonates are
room temperature amine protection reaction under neat valuable industrial raw materials and acidic ionic liquids are
conditions.587 The miscellaneous catalysis applications of excellent catalysts for the preparation of cyclic carbonates from
BAILs include: the insertion of α-diazoacetate into the N−H epoxides and carbon dioxide.143,597 A variety of acidic ionic
bonds of amines,485 regioselective thiocyanation of aromatic liquids have been shown to be good catalysts for this process,
and heteroaromatic compounds at room temperature,588 and which includes; imidazolium, pyridinium, triethanolammonium
conversion of alcohols to azides.589 protic and −SO 3 H functionalized ionic liquids, 143,598
Selective nitration of phenols is another instance where [(HO2C)2C2Ph3P][Br],599 2-(N,N-
nitration with sodium nitrate could be carried out in the dimethyldodecylammonium)acetic acid bromide,319 and car-
presence of acidic ionic liquid 1-butyl-3-methylimidazolium boxyl-isobutyl-functionalized immobilized ionic liquids.284 Xiao
hydrogen sulfate [C4C1im][HSO4] at room temperature, in and co-workers studied a series of protic ionic liquids for the
good to high yields and short reaction times.590 Furthermore, synthesis of propylene carbonate from CO2 and propylene
regioselective mononitration of chlorobenzene has been oxide as shown in Figure 31.143 The effect of protic acid ionic
investigated in the HNO3−Ac2O system with caprolactam liquid catalysts on the synthesis of propylene carbonate is
based BAILs as shown in Figure 30.591 The sequence of shown in Table 16.

Figure 31. Protic acid ionic liquid catalyzed synthesis of propylene


carbonate from propylene oxide and carbon dioxide.143
Figure 30. Caprolactam based BAIL catalyzed regioselective
mononitration of chlorobenzene591 Table 16. Effect of Protic Acid Ionic Liquid Catalysts on the
Synthesis of Propylene Carbonatea143
entry protic ionic liquid catalyst yieldc (%)
nitrification activity is [CP][HSO4] > [CP][p-TSA] > [CP]- 1 methylimidazole (C1im) trace
[BSA]. The mole ratio of chlorobenzene to ionic liquid was 2 methylimidazolium bromide [C1Him][Br] 94.5
10:1.5, at 60 °C and the reaction time was 2.5 h, the yield of 3 imidazoliumiodide [Him][I] 93.3
mononitro-chlorobenzene could reach 71.22%; and the mass 4 triethylammonium bromide [(C2)3HN][Br] 34.9
ratio of para/ortho isomer was 7.74, which was much more 5 pyridinium bromide [HPy][Br] 31.6
than 2.0 of para/ortho isomer mass ratio obtained by nitric- 6 methylimidazolium chloride [C1Him][Br] 47.4
sulfuric mixed acids as catalyst. Besides, the ionic liquid could 7 methylimidazoliumiodide [C1Him][I] 91.8
be used repeatedly.591 Acidic ionic liquid catalyzed direct 8 ethylimidazolium bromide [C2Him][Br] 85.8
nitration of 1,4,5,8-tetraaza-bicyclo-[4,4,0]-decane to synthesize 9 butylimidazolium bromide [C4Him][Br] 77.7
1,4,5,8-tetranitro-1,4,5, 8-tetraazabicyclo-[4,4,0]-decane 10b methylimidazolium bromide [C1Him][Br] 59.8
(TNAD) with N2O5 is also another interesting application.592 a
Reaction conditions: propylene oxide 5.0 mL, catalyst 1.0 mol %,
9.2. Carbon Dioxide Dissolution and Fixation CO2 1.5 MPa, 120 °C, 2.0 h. bCatalyst 0.5 mol %. cIsolated yield and
Dissolution and fixation of CO2 is an important green the selectivity >99%.
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 In another example Gao and co-workers proved that a
well-known for their good CO2 absorption characteristics.594,595 polystyrene-supported Lewis acidic iron-containing ionic liquid
Deng et al. has prepared a series of amide-based Brönsted acidic is a recyclable heterogeneous catalyst for converting CO2 into
ionic liquids by acid−base neutralization reaction of N,N- cyclic carbonates.130 Notably, the catalyst could be readily
dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), recovered and reused over five times without appreciable loss of
and N-methylpyrrolidone (NMP) with trifluoroacetic acid catalytic activity. Additionally the protocol has been applied to
(TFA) or tetrafluoroboric acid (FBA). The solubility data of reactions of aziridines/propargyl amines with CO2.130 Carboxyl
CO2 in these BAILs was determined at different temperatures functionalized dication imidazolium-based ionic liquids have
and sub atmospheric pressure using isochoric saturation also been evaluated as efficient catalysts for the synthesis of
method. In these experiments they found that, with the same cyclic carbonates from epoxides and CO2 in the absence of a
cation CO2 solubility in TFA-based BAILs are higher than that cocatalyst and a solvent.600
in FBA-based ones.594 Mumford et al. recently evaluated the 9.2.2. Urea Synthesis. Lewis acidic ionic liquids are known
protic ionic liquid ethylenediamine N,N-dimethylaminoethy- to catalyze the reaction of CO2 with amines to give ureas. Yao
lammonium formate for the removal of CO2 from N2 mixed gas et al. reported the use of [C4C1im][AlCl4] as the catalyst and
streams.596 This evaluation was conducted by comparison with solvent, for the reaction of CO2 with aniline at 160 °C,
the industrial standard 30 wt % monoethanolamine (MEA). producing 1,3-diphenyl urea in 17.9% yield and 98.9%
These studies demonstrated that the sorption process included selectivity as shown in Figure 32.601
a chemical reaction component and is comparable to MEA; 9.3. Ionogels, Electrolyte, Battery, and Capacitor
however, the mass transfer coefficient is an order of magnitude Applications
lower than MEA, which was likely due to the higher viscosity of Mizumo and co-workers reported a thermally stable, water-free
the ionic liquid and its impact on carbon dioxide diffusivity.596 proton conductor based on Brönsted acidic ionic liquid and
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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-
Figure 32. Lewis acidic ionic liquid catalyzed synthesis of 1,3-diphenyl
butylsulfonic)-3-methylimidazolium bis(trifluoromethyl-
urea. sulfonyl)imide [(HSO3)4C4C1im][NTf2], 1-(4-butylsulfonic)-
3-methylimidazolium bis trifluoromethanesulfonate
[(HSO3)4C4 C1im][OTf] and membranes based on the
silicate network.602 This material was prepared with a mixture polymerization of 1-(4-butylsulfonic)-3-vinylimidazolium tri-
of bis(trifluoromethyl sulfonyl)imide and 1-(4-butylsulfonic)-3- fluoromethanesulfonate [(HSO3)4C4(CC)im][OTf] were
methylimidazolium hydrogen sulfate by using the sol−gel tested. This is the first report that describes the application
process. The ionic conductivity of the ionogel reached 10−3 S of a polymerized protic ionic liquid membranes for fuel cells.630
cm−1 at 150 °C without any humidification.602 An alternative approach is the immersing of the membranes
Acidic ionic liquids have been studied as electrolytes for based on imidazolium ionic liquids with 1-butyl-3-methylimi-
several applications like battery electrolytes, electrophoresis dazolium dihydrogen phosphate [C4C1im][H2PO4] and
media and electroplating media.603 Rezaei et al. studied the polymers of sulfonated poly(ether−ether) ketone (SPEEK)
electrochemical and corrosion behaviors of alkyl ammonium or polyvinylidenefluoride (PVDF) into pure phosphoric acid at
hydrogensulfates as electrolyte additives on Pb alloy electrodes room temperature. A composite membrane fabricated by this
of the lead-acid battery.604 A few acidic ionic liquids such as method has achieved proton conductivity of 3.0 × 10−2 S cm−1
[(C6H5CH2)(C1)2HN][AlCl4] have been tested as electrolytes at 160 °C under anhydrous conditions.631
for batteries.605,606 Then there is an example in the use as a
9.5. Electrophoresis Applications
solar cell electrolyte, where the acidic ionic liquid polymer
poly[((3-(4-vinylpyridine) propanesulfonic acid) iodide)-co- In an interesting chromatography application N-methyl-2-
(acrylonitrile)] works as an ionic liquid electrolyte for dye- pyrrolidonium methyl sulfonate acidic ionic liquid has been
sensitized solar cells.607 The cell based on electrolyte containing used as a new dynamic coating for separation of basic proteins
20 wt % poly-AIL yielded an overall energy conversion by capillary electrophoresis.632 The authors found that AIL
efficiency of 6.95% under AM 1.5 illumination at 100 mW modified capillary not only generated a stable suppressed
cm−2.607 A number of acidic ionic liquids have been used as electro osmotic flow, but also effectively eliminated the wall
neat liquids as well as additives in electrodeposition experi- adsorption of proteins.
ments, which include: [C4C1im][HSO4],608,609 [C2py][HSO4], 9.6. Membrane Applications
[C4py][HSO4] and [C6py][HSO4] in the electrodeposition of
Acidic ionic liquid incorporated membranes are known and
zinc,610 [(C2)4N][HSO4], [(C4)4N][HSO4],611 [C4py][HSO4]
these materials are particularly useful for the separation of
and [C 6 py][HSO 4 ] in copper electrodeposition, 612,613
gases633,634 as well as incorporation of ion exchange and
[(C1)3HN][Cl],614 [(C2)3HN][Cl]615 in the electrodeposition
antibiofouling properties.635 Huang et al. reported the
of Al, [C2C1im][AlCl4] in the electrodeposition of Al−W
preparation and use of dicarboxylate-based IL incorporated
alloy616−618 and octyl-3-methylimidazolium chlorogalate in the
membranes as a class of tunable media for the selective
electrodeposition of Ga.619
separation of acidic gases.633 When the anions of dicarboxylate-
9.4. Fuel-Cell Applications based ILs are fully deprotonated, they could be used as effective
The use of acidic ionic liquids as electrolytes in fuel-cells is an carriers for the selective separation of CO2. The permeabilities
emerging field due to their high conductivity, as well as their of CO2 in triethylbutylammonium malonate
thermal, chemical and electrochemical stability.620,621,338,622 [C4(C2)3N]2[malonate] and triethylbutylammonium maleate
Yasuda et al. investigated diethylmethylammonium trifluor- [C4(C2)3N]2[maleate] under the partial pressure of 0.1 bar
omethanesulfonate [(C2)2C1HN][OTfs], which exhibits favor- range from 2147 to 2840 barrers and the permselectivities of
able bulk properties and electrochemical activity for fuel-cell CO2/N2 and CO2/CH4 in them approach to 178−265 and
applications. In this case solid thin films containing 98−221, respectively. However, when the anions of dicarbox-
[(C2)2C1HN][OTfs] were fabricated using sulfonated poly- ylate-based ILs are half deprotonated, they are efficient solvents
imide as a matrix polymer and used in nonhumidifying fuel cell for the selective separation of SO2.633 The application of
operation at 120 °C.621,623 encapsulated ionic liquids within porous moieties in the proton
Many research groups have studied the use of protic ionic exchange membranes field is described in a book chapter by
liquids as a component in composite proton exchange Eguizábal and Pina as well.636
membranes (PEMs) for the next generation fuel cells.624−626 Nafion-polymeric acidic ionic liquid composite membranes
The protic ionic liquids studied in this application include 1- with different cations have been studied for their physical
vinylimidazolium trifluoromethanesulfonate [(CH2CH)- properties.637 In general, the Nafion/polymeric IL composite
Him][OTf],627 1-methyl-imidazolium trifluoromethanesulfo- membranes exhibit a significant increase in the ionic
nate [C1Him][OTf],628 and polymer electrolyte membranes conductivities than Nafion under anhydrous conditions. The
based on poly(ethylene oxide)/1-butyl-3-methylimidazolium interactions between the Nafion ionomer and different
hydrogen sulfate [4C4C1im][HSO4].629 In another approach geometric cations of polymeric ILs were also discussed by Lu
the acid retention capability of poly(4,4′-diphenylether-5,5′- et al. in the comparison of nanostructures, dynamic-mechanical
bibenzimidazole) (OPBI) nanocomposite membranes in fuel properties, and thermal stabilities of the Nafion/polymeric IL
cells could be enhanced by incorporating protic ionic liquids.625 composite membranes.637 The molecular dynamics and ion
In this case silica nanoparticles of 25 nm size were prepared, transport studies on polymerized imidazolium-based protic
successfully modified with phosphate anion containing ionic liquid [(HSO3)4C4(CC)im][OTf] have indicated a
imidazolium AILs and were incorporated in OPBI by solution strong decoupling between conductivity relaxation times σσ
blending method.625 (related to the ions migration through the polymer matrix) and
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segmental dynamics when the ionic transport is controlled by comprising acidic ionic liquid N,N-dimethylacetamide meth-
fast proton hopping through the dense hydrogen-bond anesulfonate, Ru/C, and formic acid as shown in Figure 34.658
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
Figure 34. One-pot conversion of lignocellulosic and algal biomass
into 2,5-dimethylfuran (DMF)658
diethylmethylammonium triflate [(C2)2C1HN][OTf] doped 639
Nafion membrane
triethylammmonium triflate [(C2)3HN][OTf] doped Nafion- 640,641,639
membranes Cellulose can be depolymerized to glucose and then
diethylmethylammonium triflate [(C2)2C1HN][OTf] proton 621 dehydrated to HMF in one-pot using acidic ionic catalysts.659
conductivity Ding et al. reported the catalytic conversion of microcrystalline
alkylammonium hydrogensulfate [RH3N][HSO4] in 642,643 cellulose (MCC) to HMF using CuCl2 in 1-(4-butylsulfonic)-3-
permeation of chromium(III) using ionic liquid and
pseudoemulsion hollow fiber strip dispersion. methylimidazolium hydrogen sulfate [(HSO 3) 4C4 C1 im]-
N,N-dimethylpyrrolidinium methylphosphite membrane 644 [HSO4] in 69.7% yield.660 In an example using raw biomass,
[(C1)2Pyrr][MeHPO3] for the separation of acetylene/ the carbohydrate-rich weed species foxtail weed was directly
olefin mixtures 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
9.7. Conversion of Biomass to Renewable Feedstock In the C5 sugar platform, Serrano-Ruiz et al. reported the
Chemicals dehydration of xylose to furfural using −SO3H functionalized
9.7.1. Renewable Furans, Levulinic Acid, and Related acidic ionic liquids under microwave heating.662 In another
Compounds. Acidic ionic catalyzed dehydration of carbohy- example, Tao and co-workers reported the 1-(4-butylsulfonic)-
drates to 5-hydroxymethylfurfural, furfural, and levulinic acid 3-methylimidazolium hydrogen sulfate [(HSO3)4C4C1im]-
and related compounds has emerged as an active research area [HSO4] catalyzed dehydration of xylose into furfural under
in the last 4−5 years due to the current interest in renewable mild conditions. A xylose conversion of 95.3% with a furfural
feedstocks and fuels. Dehydration of carbohydrates to furan yield of 91.45% was achieved in a 25 min reaction time at 150
derivatives is the most widely studied reaction, and the °C.663
common dehydration of fructose to 5-hydroxymethylfurfural 4-Oxopentanoic acid or levulinic acid is a renewable
(HMF) occurs via elimination of three molecules of water as generation key chemical that can be derived from C5 and C6
shown in Figure 33. 645,646 Acidic ionic liquids 1-(4- carbohydrates via a series of dehydration/hydration reactions
butylsulfonic)-3-methylimidazolium hydrogen sulfate,647,648,350 and acidic ionic liquids have been used as catalysts for the
1-(4-butylsulfonic)-3-allylimidazolium hydrogen sulfate trifluor- preparation of levulinic acid and related compounds. High
omethanesulfonate,649 N-methyl-2-pyrrolidonium hydrogen molecular weight cellulose has been converted to a mixture of
sulfate,329 1-methyl-3-(butyl-4-chlorosulfonyl) imidazolium ethyl levulinate and levulinic acid by using 1-(3-propylsulfonic)-
chlorosulfate,650 1-ethyl-3-methylimidazolium hydrogen sul- 3-methylimidazolium chloride [(HSO3)3C3C1im][Cl] as the
fate,651 dimethylimidazolium hydrogensulfate,652,653 dimethyl- catalyst in aqueous ethanol medium in a one-pot operation
benzaimidazolium hydrogensulfate,652 1-carboxymethyl-3- under mild conditions as shown in Figure 35.664 The highest
methyl imidazolium chloride,654 1-carboxypropyl-3-methyl ethyl levulinate yield of 19.0% was obtained for a reaction
imidazolium chloride,655 and Cr3+ containing SO3H-function- carried out at 170 °C, for 12 h, in water−ethanol medium
alized polymeric BAILs656 have been reported as catalysts. containing 38.5% water. The levulinic acid yields continues to
Acidic ionic catalyzed dehydration of D-glucose to 5- increase with increasing water content up to about 54% water
hydroxymethylfurfural is also known.657 Amarasekara and in aqueous ethanol for reactions carried out at 150 °C for 48 h,
Razzaq have proposed a mechanism for 1-(1-propylsulfonic)- and the highest levulinic acid yield was 23.7%. The BAIL
3-methylimidazolium chloride catalyzed transformation of D- catalyst could be efficiently recovered (96%) from the water
glucose to HMF using NMR studies of C-1 and C-2 13C labeled phase with negligible contamination and the stability of the
D-glucose. The proposed mechanism involves an isomerization catalyst was confirmed by comparison of the 1H NMR
of D-glucose to D-fructose via open chain forms during the spectrum of the recovered catalyst with fresh catalyst.664
dehydration reaction.645 In another example cellulose has been liquefied in ethylene
In a related example, one-pot conversion of lignocellulosic glycol at 180 °C, using 6.7 mol % 1-(3-propylsulfonic)-3-
and algal biomass into a liquid fuel 2,5-dimethylfuran (DMF) methylimidazolium chloride [(HSO3)3C3C1im][Cl] and 1-(4-
has been achieved by using a multicomponent catalytic system butylsulfonic)-3-methylimidazolium hydrogen sulfate

Figure 33. Brönsted acidic ionic liquid catalyzed transformation of D-fructose to 5-hydroxymethylfurfural (HMF).

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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 The catalytic performances of AIL containing HSO4− anion
only three compounds as shown in Figure 36, which were 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
Figure 36. 1-(3-Propylsulfonic)-3-methylimidazolium chloride was liquefied to a mixture of biomass derived furan-acetone
[(HSO3)3C3C1im][Cl] and 1-(4-butylsulfonic)-3-methylimidazolium aldol condensation products using [(HSO3)3C3C1im][Cl] or
hydrogen sulfate [(HSO3)4C4 C1im][Cl] catalyzed liquefaction of [(HSO3)4C4C1im][Cl] as the BAIL catalyst under moderate
cellulose in ethylene glycol. 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
identified as 2-hydroxyethyl levulinate, 2-hydroxyethyl levuli- compounds, some selected examples and their references are
nate ethylene ketal, and 2,3,6,7-tetrahydro-cyclopenta[1,4]- shown in Table 18.
dioxin-5-one.665 The composition of the three components 9.7.2. Depolymerization of Cellulose. Ionic liquids with
reaches a steady state after 20 h reaction at 180 °C with 2- built-in −SO3H acid functionality is an emerging class of
hydroxyethyl levulinate: 2-hydroxyethyl levulinate ethylene biomass processing systems,676 whereas relatively milder acidic
ketal: 2,3,6,7-tetrahydro-cyclopenta[1,4]dioxin-5-one molar ionic liquids like 1-butyl-3-methylimidazolium hydrogensulfate
percentage ratio of approximately 47:22:31.665 are used in partial depolymerization and preparation of

Figure 37. Application of acidic ionic liquids in liquefaction of sawdust in polyethylene glycol 400-glycerol mixtures668

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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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Table 20. Selected Examples of Application of Acidic Ionic Liquids in Hydrolysis of Cellulose and Cellulosic Biomass
acidic ionic liquid catalyst(s) hydrolysis of polysaccharide/biomass and conditions refs
1-propyl sulfonic acid-2-phenyl imidazoline hydrogensulfate and 1- butyl sulfonic acid-2- cellulose, 100 °C, 60 min. 85.1% TRS yield 687
phenyl imidazoline hydrogensulfate
[(HSO3)3C3C1im][HSO4], [(HSO3)3C3C1im][OTs] and [(HSO3)3C3C1im][Cl] hardwood hemicellulose, 160 °C to give C5 sugars (xylose + 688
arabinose) in 87% yield
[(C1Him][Cl] soybean straw and corn straw, 70 °C, 120 min. 689
[(HSO3)3C3(C2)3N][HSO4] cellulose, 100 °C, 99% TRS yield 679
[(HSO3)4C4C1im][HSO4] cellulose, sawdust, 80−120 °C 690,691
[(HSO3)3C3C1im][Cl] immobilized on silica cellulose, 70 °C, glucose and TRS in 26 and 67% yields 225
respectively
[(HSO3)3C3(CC)im][OTf] polymer cellulose, 100 °C, 77% yield 692
[(HSO3)4C4C1im][Cl] switchgrass, 70 °C for 2 h, 58. One %TRS and 15. Three % 693
glucose yields
1,1,3,3-tetramethylguanidinium hydrogensulfate cellulose, 26% glucose and 72% TRS yields 694
[(HSO3)3C3C1im][Cl] immobilized on polystyrene cellulose, 160 °C, 3 h, glucose, TRS in 21.7 and 50.1% yields 282,695
respectively
[(HSO3)3C3C1im][Cl] and [(HSO3)4C4C1im][Cl] cellulose, 140−180 °C, 3 h 683
[(HSO3)4C4N2(CH2)3]3−nHnPW12O40 cellulose 696
[(HSO3)3C3C1im][HSO4].1/3Cr cellulose, 94% TRS yield 695
[(HSO3)3C3C1im][Cl] immobilized on biochar with ZnCl2 and CuCl2 cellulose and bamboo 697,698

Later, Liu et al. as well as Feng et al. also reported the use of series of −SO3H functionalized imidazolium, pyridinium,
Brö nsted acidic ionic liquids for catalysis of cellulose trialkylammonium BAILs have revealed that single −SO3H
depolymerization under mild conditions.679,680 However, their attached imidazolium catalysts are more effective than
approach is somewhat different from the earlier group, where pyridinium and trialkylammonium types in cellulose hydrolysis
Liu et al. first dissolved cellulose in the neutral ionic liquid in water at moderate temperature−pressure conditions.683 A
1-nbutyl-3-methylimidazolium chloride to make a 5% solution, number of research groups have studied acidic ionic liquids
and then Brönsted acidic ionic liquid and a controlled amount immobilized on a solid supports, which include; graphene-like
of water was added to hydrolyze cellulose. Furthermore, a series nanoporous carbons,684 silica,225,233 and polystyrene282 for the
of −SO3H group functionalized imidazolium and triethylam- depolymerization of cellulose as well as various lignocellulosic
monium Brönsted acidic ionic liquids were used as catalysts in biomass forms.
the Liu et al.’s study.679 They found that all of the Brönsted Acidic ionic liquid catalysts have been tested for liquefaction
acidic ionic liquids studied are effective in hydrolysis of of untreated lignocellulosic biomass samples as well, and these
cellulose, with the maximum total reducing sugar (TRS) yields experiments often produced complex mixtures of products.
over 83% at 100 °C. Acidic ionic liquids with analogous Long and co-workers used a −SO3H, −COOH functionalized,
structures showed similar catalytic activities and (3-propylsul- and HSO4-paired imidazolium ionic liquid as catalysts for
fonic)-triethylammonium hydrogen sulfate showed the highest bagasse liquefaction in hot compressed water. Using −SO3H
activity in this study. Interestingly, acid group functionalized functionalized ionic liquid at 542 K, 96.1% of bagasse could be
acidic ionic liquids can be used as catalysts in aqueous media as liquefied and 50.6% was selectively converted to low-boiling
well under moderately high temperature−pressure conditions biochemicals.685 In another experiment a series of AILs
with or without a cocatalyst. Amarasekara and Wiredu studied containing HSO4− and imidazolium cation were used in the
the catalytic activities of dilute aqueous solutions of 1-(3- liquefaction of Chinese fir sawdust in 1-octanol. This
propylsulfonic)-3-methylimidazolium chloride for the hydrol- experiment showed that the liquefaction rate could be gradually
ysis of pure cellulose by comparison with p-toluenesulfonic acid improved with the AILs of increasing acidity, and reached
and sulfuric acid.681 In this study dilute aqueous solutions of 1- 71.5% when 1-(4-butylsulfonic)-3-methylimidazolium hydro-
(3-propylsulfonic)-3-methylimidazolium chloride and p-tolue- gen sulfate was used as the catalyst at 423 K, with the 6:1 mass
nesulfonic acid are shown to be better catalysts than aqueous ratio of 1-octanol to sawdust.667 Zhuo et al. recently reported
sulfuric acid of the same H+ ion concentration for the the synthesis of a series of 2-phenyl-2-imidazoline based acidic
degradation of cellulose at moderately high temperatures and ionic liquids and used as catalysts for the hydrolysis of cellulose
pressures. For example, Sigmacell cellulose (DP ∼ 450) in in 1-butyl-3-methylimidazolium chloride.686 They noted that
aqueous solutions of 1-(1-propylsulfonic)-3-methylimidazolium BAILs with anions HSO4− and Cl− showed better catalytic
chloride, p-toluenesulfonic acid, and sulfuric acid of the same performance for the hydrolysis of cellulose than those with
acid strength (0.0321 mol H+ ion/L) produced total reducing H2PO4−.686 Selected recent examples in the hydrolysis of
sugar (TRS) yields of 28.5, 32.6, and 22.0% respectively, after cellulose and cellulosic biomass using acidic ionic liquids are
heating at 170 °C for 3.0 h. In the same set of experiments 22.2, shown in Table 20.
21.0, and 16.2% glucose yields were attained in 1-(1- The addition of some metal ions699−701 and zeolites702 as
propylsulfonic)-3-methylimidazolium chloride, p-toluenesul- cocatalysts are also known to enhance the BAIL catalyzed
fonic acid, and sulfuric acid mediums, respectively.681 In hydrolysis of cellulose in neat and in aqueous media. In a recent
addition, hydrolysis of a cellulose model compound in water development the effect of eight metal ions, Cr3+, Mn2+, Fe3+,
also supported the observation of enhanced catalytic activity of Co2+ Ni2+, Cu2+, Zn2+, and La3+ on 1-(1-propylsulfonic)-3-
−SO3H functionalized imidazolium BAILs in water in methylimidazolium chloride acidic ionic liquid catalyzed
comparison to H2SO4.682 Structure−activity relationships in a hydrolysis of cellulose in water at 140−170 °C was reported.700
6160 DOI: 10.1021/acs.chemrev.5b00763
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Table 21. Recent Applications of Acidic Ionic Liquids in Biodiesel Synthesis


acidic ionic liquid catalyst(s) starting material, biodiesel % yield refs
[C4C1im][HSO4] and [C4C1im][OTf] waste cooking oil, 95.65%. Sewage sludge 713,714
lipids, 90%
[(HSO3)3C3(CC)im][H2PO4] polymer vegetable oil, 94.2% 220
[(HSO3)3C3C1im][HSO4] immobilized on magnetic nanoparticles soybean oil with short-chain alcohols 239
[(HSO3)4C4C1im][HSO4] -Fe2(SO4)3 Camptotheca acuminata seed oil, 95.7% 189
[(HSO3)4C4C1im][Cl] jatropha curcas oil, 93.9% 715
3-butyl-6-sulfo-1-(4-benzylsulfonic)-1H-imidazolium hydrogen sulfate Nigella sativa seed oil with methanol 716
[(HSO3)3C3pyr][HSO4] immobilized on polymer waste cooking oil, 99.0% 215,213,214
[(HSO3)4C4 (alkyl)im][OTf] immobilized on silica glycerol trioleate with methanol 227
[(HSO3)3C3(C2)3N][Cl].0.67FeCl3 waste cooking oil, 95% 192
[(HSO3)4C4C1im][HSO4], [(HSO3)3C3C1im][HSO4] and 1-methyl-2-(4-butylsulfonic)- soybean oil and citrullus colocynthis oil 717−719
pyrazolium hydrogensulfate
[(HSO3)3C3(C2)3N][HSO4] soybean oil with methanol, 93.2% 720
[(HSO3)4C4pyr][HSO4] soybean oil and methanol, 94.5% 721
[(C2)3HN][HSO4] and [C4Him][HSO4] palm oil 722,723

It is interesting to note that certain transition metal ions like depolymerized and subsequently dissolved in the ionic liquid.
Mn2+, Fe3+, and Co2+ as cocatalysts produced significant This process occurred more quickly at higher temperatures,
enhancements in total reducing sugar (TRS) yields, with Mn2+ although at the highest temperatures tested significant cellulose
showing the highest activity. During these BAIL catalyzed degradation also occurred.707 Then there are few other biomass
cellulose hydrolysis in water, using Mn2+ as cocatalyst produced forms that have been tested with aqueous acidic liquid
91.8, and 91.9% TRS yields, whereas samples without Mn2+ pretreatments, which include pretreatment of corn stover
gave 28.0 and 28.7% yields at 160 and 170 °C, respectively.700 using [C1C2im][HSO4],171 microalgae using n-butyl-3-methyl-
9.7.3. Depolymerization of Lignin. In addition to the imidazolium hydrogen sulfate,708 hybrid aspen and Norway
hydrolysis of polysaccharide components acidic ionic liquids spruce using [C1C4im][HSO4],709 and microwave pretreatment
have been used as acid catalysts for the depolymerization of of eucalyptus [C1C4im][HSO4].710
lignin fraction in a number of biomass materials. Ekerdt and co- 9.8. Biodiesel Synthesis
workers separated the lignin from Oak wood by dissolving in
the neutral ionic liquid 1-methyl-3-ethylimidazolium acetate Biodiesel is the fatty acid methyl ester product formed by trans-
and subsequent precipitation. This was successfully depoly- esterification of vegetable oils or animal fats with methanol. The
merized in the acidic ionic liquid 1-H-3-methylimidazolium trans-esterification reaction can be catalyzed by bases or
chloride under mild conditions (110−150 °C).703 Furthermore, acids.711 A fair number of researchers have studied the option
of using homogeneous and immobilized forms of Brönsted
gel permeation chromatography results, showed that an
acidic ionic liquid catalysts for this trans-esterification reaction
increase in temperature from 110 to 150 °C increased the
due to possibilities like low catalyst loading and recycling of the
rate of reaction, but did not significantly change the final size of
catalyst. In 2012 Amin, Fauzi and Hafiidz published a review
the lignin fragments.703 In model compound studies, the same
article titled “An overview of ionic liquids as solvents in
research group showed that β-O-4 bonds of both guaiacylgly-
biodiesel synthesis” with 138 references summarizing the
cerol-β-guaiacyl ether and veratrylglycerol-β-guaiacyl ether
progress in this area until late 2011.712 More recent and after
undergoes catalytic hydrolysis to produce guaiacol as the
2012 applications of acidic ionic liquids in biodiesel synthesis
primary product with more than 70% yield at 150 °C.704,327
are shown in Table 21.
Long and co-workers examined the liquefaction of sugar cane
bagasse lignin using acidic ionic liquid 1-(4-butylsulfonic)-3- 9.9. Desulfurization of Gasoline, Diesel, and Petroleum
methyl imidazolium hydrogen sulfate [(HSO3)4C4C1im]- Refinery Applications
[HSO4]. They showed that more than 65% of liquefaction The removal of cyclic sulfur compounds and nitrogen
can be achieved under optimized conditions, yielding 13.5% of compounds such as thiophene (TS), dibenzothiophene
useful aromatic fine chemicals such as phenol, 4-ethylphenol, (DBT), carbazole, pyridine, and their derivatives from gasoline
and guaiacol.705 and other fuel oils is another application in acidic ionic
9.7.4. Pretreatment of Biomass. Pretreatment of biomass liquids.212,724−726 A number of common Brönsted and Lewis
as a preparation for enzymatic hydrolysis is another application acid ionic liquids have been tested for hydrodesulfurization and
of acidic ionic liquids. In this application dilute aqueous hydrodenitrogenation processes, which includes dialkylpyridi-
solutions of acidic ionic liquids are often used under mild nium tetrachloroferates and [C1C6im][FeCl4],727,728 1-methyl-
conditions. The selective hydrolysis of hemicellulose fraction is imidazolium hydrogen sulfate [C1Him][HSO4], N-methylpyr-
known in using BAIL based pretreatments.706 Cox and Ekerdt rolidinium hydrogen sulfate [C1HPyrr][HSO4],729 [C1C4im]-
have shown that acidic ionic liquid 1-H-3-methylimidazolium [HSO4],730,731 [(HSO3)2C2C1im][HSO4].732,733 N-methyl-
chloride can be used for effective pretreatment of yellow pine pyrrolidonium tetraflouoroborate [C 1 HPyrr][BF 4 ], 734
wood chips under mild conditions.707 In this study wood [C4C1im][FeCl4],735 and [(COO)C1C1im][HSO4].382
samples were treated between 110 and 150 °C for up to 5 h in Chen and co-workers demonstrated that Lewis acidic ILs 1-
the ionic liquid and three fractions were collected; a cellulose butyl-3-methylimidazolium chloride with IL: ZnCl2 1:1 and 1:2
rich fraction, lignin, and an aqueous fraction. This treatment mol ratios as well as Brönsted acidic ILs [C4C1im][HSO4] and
caused the hemicellulose and the lignin to be degraded and [C4C1im][HSO4], Lewis-Brönsted acidic IL N-methylpyrroli-
dissolved from the cell walls of the pine wood. The lignin was donium zinc chloride with IL: ZnCl2 mole ratios 2:1 to 1:2 can
6161 DOI: 10.1021/acs.chemrev.5b00763
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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
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organic soluble sulfonic acids like p-toluene sulfonic acid and Lanka, his Ph.D. in organic chemistry from City University of New
fluorinated super acids. Now the same reactions are being York (with William. F. Berkowitz, 1985), completed his postdoctoral
tested again with BAILs and in many cases the BAILs have training at Bar-Ilan University in Israel (with Alfred Hassner, 1985-87),
shown superior catalytic properties in comparison to organic and spent two years at the Center for Molecular Architecture at
sulfonic acids and mineral acids. This may be due to organic Central Queensland University in Rockhampton, Australia as a visiting
soluble nature and interactions of charged intermediates with scientist with Ronald Warrener. In 2009, professor Amarasekara’s
cation/anion in BAIL that allows facile proton or electron research group introduced the use of sulfonic acid group functionalized
transfers with acidic ionic liquids. Brönsted acidic ionic liquids for the direct hydrolysis of untreated
The use of BAILs in biomass processing research is an cellulose and lignocellulosic biomass to glucose and its oligomers. The
important turning point. The introduction of sulfonic acid current research interests of his group are acidic ionic liquid based
group functionalized acidic ionic liquids in the depolymeriza- catalysis and the development of chemocatalytic methods for the
tion of cellulose in 2009 has opened a new branch of research processing of biomass to renewable fuels and feedstock chemicals. He
with a vast potential and industrial applications.678 The rapid is the author of the book “Handbook of Cellulosic Ethanol” (Wiley -
progress in this arena since the introduction of AILs in biomass Scrivener 2013) and has published more than 100 peer reviewed
processing has been reviewed by da Costa Lopes and Bogel- research articles.
Łukasik in the March 2015 review titled “Acidic ionic liquids as
sustainable approach of cellulose and lignocellulosic biomass ACKNOWLEDGMENTS
conversion without additional catalysts”.77 The future of acidic Author thanks NSF Grants CBET-0929970, CBET-1336469,
ionic liquids as biomass processing catalysts is bright, and one and HRD-1036593 for financial support.
possibility is the development of an ionic liquid based small
molecular mimic for cellulase enzyme. The BAIL catalyst has ABBREVIATIONS
the features of the enzyme; it can bind with cellulose via
hydrogen bonds, and if the orientation is correct it can deliver AIL acidic ionic liquid
the acidic proton to glycosidic bond of cellulose promoting the BAIL Brönsted acidic ionic liquid
hydrolysis, like the cellulase enzyme. However, a lot more work DP degree of polymerization
is needed in the area of BAIL−cellulose binding mechanisms DPA diphenolic acid
using experimental and computational tools. DTBP di tbutyl phenol
The second highlighted area is the ionic conductivity aspects EL ethyl levulinate
of acidic ionic liquids. The earliest known application of this HMF 5-hydroxymethylfurfural
property is the use of Lewis acidic ionic liquids with metal salts LA levulinic acid
like AlCl3 for the electrodeposition of Al, which generally LAIL Lewis acidic ionic liquid
require high melting salt baths without the use of ionic liquid MEA mono ethanol amine
based systems. Then more recent developments are in ion MPa mega Pascal
conducting membranes and electrolytes in fuel cells as well as OBs benzenesulfonate
in batteries, and these uses are in the verge of commercial OTs toluene sulfonate
applications. OTf trifluoromethanesulfonate
Overall, acidic ionic liquids have grown onto their own sub PAIL protic acidic ionic liquid
discipline with vast array of applications. Some of the research TBC tbutyl catechol
in this area is geared toward technologies likely to replace the TBP tbutyl phenol
use of noble metal on chlorinated alumina for reforming and TEOS tetraethyl orthosilicate
CoMo/NiMo catalysts for desulfurization of gasoline, by the Tfa trifluoroacetate
use of acidic ionic liquids as catalysts. Another possible TOF turnover frequency
application is replacement of mineral acids in alkylation TON turnover number
processes. However, the cost of these new materials are much TRS total reducing sugar
higher than H2SO4 or HF; hence, the overall benefits of using
AILs depends on efficiency improvements as well as the REFERENCES
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6183 DOI: 10.1021/acs.chemrev.5b00763


Chem. Rev. 2016, 116, 6133−6183