Professional Documents
Culture Documents
Review
A R T I C L E I N F O
A B S T R A C T
Article history:
Received 20 May 2009
Received in revised form 11 September 2009
Accepted 6 October 2009
Available online 12 October 2009
This review gives a survey on the latest most representative developments and progress concerning ionic
liquids, from their fundamental properties to their applications in catalytic processes. It also highlights
their emerging use for biomass treatment and transformation.
2009 Elsevier B.V. All rights reserved.
Keywords:
Ionic liquids
Biphasic catalysis
Supported Ionic Liquid Catalysis (SILC)
Task specic ionic liquids (TSIL)
Protic ionic liquids (PILs)
Thermoregulated ionic liquids
Biomass
Lignocellulose
Cellulose
Contents
1.
2.
General introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Ionic liquids: properties, evolution and next generations . . . . . . . . . . . . . . . .
2.1.
Properties of ionic liquids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
A widening range of ionic liquids available. . . . . . . . . . . . . . . . . . . . . .
2.2.1.
General remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.2.
Protic ionic liquids (PILs). . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.3.
(Multi)-functional ionic liquids . . . . . . . . . . . . . . . . . . . . . . . .
2.2.4.
Chiral ILs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.5.
Switchable-polarity solvents (SPS) . . . . . . . . . . . . . . . . . . . . .
2.2.6.
ILs at the frontier between organic and inorganic materials.
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3
3
3
5
5
7
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10
11
11
Abbreviations: IL(s), ionic liquid(s); [BMI]+, 1-butyl-3-methylimidazolium; [BMMI]+, 1-butyl-2,3-dimethylimidazolium; [MMI]+, 1-methyl-3-methylimidazolium; [HMI]+, 1hexyl-3-methylimidazolium; [OMI]+, 1-octyl-3-methylimidazolium; [AMI]+, 1-allyl-3-methylimidazolium; [AEI]+, 1-allyl-3-ethylimidazolium; [MI]+, 1-methyl-3-Himidazolium; [BMPy]+, N-butyl-3-methylpyridinium; [BPy]+, N-butylpyridinium; [PrMI]+, 1-propyl-3-methylimidazolium; [BMP]+, N-butyl-N-methylpyrrolydinium;
[PMP]+, N-propyl-N-methylpyrrolidonium; [NTf2], bis(triuoromethylsulfonyl)amide (CF3SO2)2N; [OTf], triuoromethylsulfonate CF3SO3; [OMs], mesylate CH3SO3;
[Fm], formate HCOO; [Ac], acetate CH3COO; TPPTS, triphenylphosphine trisulfonate sodium salt; TPP, triphenyphosphine; PEG, poly(ethylene glycol); LAB, linear alkyl
benzene; COD, 1,3-cyclooctadiene; SWNT, single wall carbon nanotube; TSIL, task specic ionic liquid; SILP, supported ionic liquid phase catalysis; PSIL, polystyrene
supported ionic liquids; SPS, switchable polarity solvent; PTC, phase transfer catalysis; LSER, linear solvation energy relationship; MD, molecular dynamics; DFT, density
functional theory; QSAR, quantitative structureanalysis relationship; HDS, hydrodesulphuration process; MAO, methylaluminoxane; CIL, chiral ionic liquid; PIL, protic ionic
liquid; DMSO, dimethylsulfoxide; DMAc, dimethylacetamide; PPN, bis(triphenylphosphorylidine)ammonium cation; DBU, 1,8-diazabicyclo-[5.4.0]-undec-7-ene; DABCO,
1,4-diazabicyclo[2.2.2]octane; REACH, registration, evaluation and authorisation of chemicals; EINECS, european inventory of existing commercial chemical substances;
EXAFS, extended X-ray absorption ne structure; ESI-MS, electrospray ionization-mass spectrometric; NOESY, nuclear overhauser enhancement spectroscopy; HOESY,
heteronuclear version of the NOESY experiment; ROESY, rotating frame overhauser effect spectroscopy.
* Corresponding author. Tel.: +33 4 78 02 28 89; fax: +33 4 78 02 20 66.
E-mail addresses: helene.olivier-bourbigou@ifp.fr (H. Olivier-Bourbigou),
lionel.magna@ifp.fr (L. Magna), didier.morvan@ifp.fr (D. Morvan).
1
Tel.: +33 4 78 02 28 86; fax: +33 4 78 02 20 66.
2
Tel.: +33 4 78 02 38 74; fax: +33 4 78 02 20 66.
0926-860X/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2009.10.008
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51
1. General introduction
Ionic Liquids (ILs) have attracted rising interest in the last
decades with a diversied range of applications (Fig. 1). The types
of ionic liquid available have also been extended to include new
families and generations of ionic liquids with more specic and
targeted properties. This expanding interest has led to a number of
reviews on their physico-chemical properties, the design of new
families of ionic liquids, the chemical engineering and the wide
range of arrangements in which ILs have been utilised (liquid
phase, multiphase, immobilized on supports, . . .) and pilot or
industrial developments [1].
Why ILs have attracted so much attention in the last few decades?
In addition to the fact that they are now commercially available,
there is a better understanding of the effect of ionic liquids
(chemical and physical properties as well as engineering uids).
Consequently, ionic liquids have been used more widely and
efciently, with better control over the overall process. The
introduction of structural functionalities on the cationic or anionic
part has made it possible to design new ILs with targeted
properties [2]. More recently, ILs appear to be the subject of
fundamental publications aimed at improving the understanding
of these solvents, predicting their physico-chemical properties and
publications describing their use in increasingly diverse applications such as sensors, fuel cells, batteries, capacitors, thermal
uids, plasticizers, lubricants, ionogels, extractants and solvents in
analysis, synthesis, catalysis and separation, to name just a few.
Some new applications, such as energetic compounds or pharmaceutical ILs, are still emerging. ILs can be used as more than just a
alternative green solvents. They differ from molecular solvents
by their unique ionic character and their structure and organisation which can lead to specic effects. They are tuneable,
multipurpose materials.
When reading papers on ILs, one of the key words is diversity.
Diversity of anioncation combinations, diversity of modes of
preparation, modes of purication and nature of impurities
(quality), diversity of properties, diversity of mode of use, diversity
of applications. This is one of the reasons why it is so difcult to
make generalisations about their physical properties or their use.
The contribution ILs make to homogeneous catalysis has more to
do with the enhancement of catalytic performances (activity,
selectivity or new chemistry) and the possibility of catalyst
separation and recycling by immobilization in the IL-phase than
with environmental concerns. They can act as solvents, as
multifunctional compounds like solvents and ligands, solvents
and catalysts, stabilising agents for the catalysts or intermediates.
4
Table 1
General reviews on ILs (from 2003 to 2008).
General (catalysis)
Task-specic ILs
ILs in catalysis
Catalysis in ILs
Homogeneous catalysis in ILs
Catalysis in ILs
Transition metal-catalysed reactions in
non-conventional media
The path ahead for ILs
Applications of ILs in the chemical industry
Catalysts with ionic tag and their use in ILs
Specic reaction/topic (catalysis)
Polymerization processes in ILs
Supported ionic liquid phase (SILP) catalysis
Oxidations of organic compounds in ILs
Functionalised imidazolium salts for TSILs
and their applications
Olen hydroformylation in ILs
Brnsted acids in ILs
Enantioselective catalysis in ILs
Asymmetric synthesis in ILs
Lanthanides and actinides in ILs
ILs in separations
Olen metathesis in ILs
Palladium-catalysed reactions in ILs
ILs towards supercritical uid applications
ILs in heterocyclic synthesis
Applications of chiral ILs
Synthesis and application of chiral ILs
Electrochemical reactions in ILs
Bio-catalysis/biomass
Biocatalysis in ILsadvantages beyond green technology
Biocatalytic transformations in ILs
ILs: Green solvents for nonaqueous biocatalysis
Chemical and biochemical transformations in ILs
Biocatalysis in non-conventional media (ILs, scFluids.)
Biocatalysis in ILs
Ionic green solvents from renewable resources
Oxidoreductase behaviour in ILs
Biotransformations and organocatalysis with ILs
Dissolution and functional modication of cellulose in ILs
Synthesis (inorganic & organic)
Metal-containing ILs and ILs crystals based on
imidazolium moiety
ILs solvent properties and organic reactivity
Application of zeolites in supercritical uids and ILs
The phosphorus aspects of green chemistry
Application of ILs in polymer science
Analysis
ILs in chromatographic and electromigration techniques
Year
Ref.
2004
2004
2006
2007
2007
2007
[4]
[5]
[6]
[7]
[8]
[9]
2007
2008
2008
[10]
[11]
[12]
2004
2006
2006
2006
[13]
[14]
[15]
[16]
2007
2007
2007
2007
2007
2007
2008
2008
2007
2008
2008
2008
2008
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
2003
2003
2005
2005
2007
2007
2007
2008
2008
2008
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
2005
[40]
2005
2007
2007
2009
[41]
[42]
[43]
[44]
2008
[45]
There has been an increased interest for ILs that present better
inertness under reaction conditions. The hydrolysis of [PF6] or
[BF4] anions to generate HF in situ has been the object of
numerous reports. Reactions catalysed by protic acids have often
been described in [PF6] based ILs, probably thanks to the presence
of HF. The formation of transition metal uoride under certain
conditions has also been observed [70,71]. The ionic liquid based
on the [(C2F5)3PF3] anion has been recently proposed as a more
chemically stable alternative to [PF6] [72].
The activation of the C(2)-H of the imidazolium to lead to the
N-heterocyclic carbene (NHC) in presence of base is also largely
described [73]. Consequently, increased interest has been found
in phosphonium ILs because of their higher stability under
basic conditions, such as in Grignard reactions [74]. To protect
the acidic C(2)-H, 2-methylimidazole based ILs are often used.
By analogy, methimazole based ILs have been described in
which the C(2) proton is replaced by a thiol linkage (Scheme 3)
[75].
The latest applications of ILs concern ILs with biological
properties (Scheme 4) [76]. Hypergolic fuels in which hydrazine
(3) Cost and biodegradability have also been a main concern and
new families of ILs derived from renewable feedstock or from
low cost starting materials have been described (Scheme 5).
These Bio-ILs are entirely composed of biomaterials [78]. An
example is given by the development of the deep eutectic
mixtures liquid systems based on chloline chloride [79] for
which the qualication of ionic liquids is still the subject of
controversies. Choline can be used as alternative cation in
combination with suitable anion to generate ILs (choline
salicylate melts at 50 8C and was described in 1960). The
physical properties (viscosity, melting point, thermal stability,
polarity) of different carboxylate anions such as acetate, tartrate,
lactate, succinate, glycolate, maleate coupled with choline cation
have been described. Surprisingly glycolate presents a Tm of
38 8C. The thermal stability range of the series is 183223 8C
[78]. The maleate gives moderate viscosity. Other interesting ILs
based on choline cations have been prepared by direct
neutralisation of choline hydroxide with different aromatic or
cyclic aliphatic carboxylic acids (Scheme 6). Surprisingly, some
of these ILs show low Tg and Tm. The biodegradability properties
of these ILs have been reported [80]. Very recently, it was shown
that the incorporation of ester side chain moiety on pyridinium
or nicotinium cation could lead to biodegradable ILs contrary to
the pyridinium analogues ILs [81].
(4) New materials have been developed using imidazolium as
backbone to access to functional silica gels or carbon nanotubes
with exible properties [82]. The IL is immobilized on the solid
support by covalent bonds generally between the silyl group
and the imidazolium cation. The immobilization of metal ions
on silica surface offers a novel class of materials where the
environment of the metal is comparable to that found in of the
type [BMI]2[MX4] [83].
(5) ILs recyclability [84] becomes one of the main issues when
process developments are envisioned: distillable ILs (under
relatively normal pressure and temperature conditions) or ILs
presenting low thermal stability have been designed. These ILs
can contain a weakly basic anion and a cation formed from a
tertiary amine and an exchangeable proton (Scheme 7). By
distillation, the neutral acid or base (if volatile enough) can be
separated from the ionized species. They can subsequently be
recombined to reform the IL. There is a vast number of cation
anion combination of such protic ILs. Carbamate based ILs form
another class of distillable ILs (see switchable solvents). Each
application requires specic properties, there is no ILs that can
satisfy all of them. We will focus here on the last developments.
2.2.2. Protic ionic liquids (PILs)
While one of the rst IL, described in 1914 by Walden [85], was of
the protic type [EtNH3][NO3] (with a mp = 12.5 8C, described in
nearly all reviews on ILs!), aprotic ILs largely dominate the open
literature due to their inertness relative to organometallic compounds and their potential of applications, particularly in catalysis.
However, there has been a resurgence of interest for these Protic ILs
essentially because of their great potential for proton transfer
applications in fuel cell technologies. A review was written by Poole
including the use of these Protic ILs in chromatography [86]. Some of
these ILs present low melting points (well below 100 8C) and high
conductivities (over 102 S cm1 at 130 8C) [87]. Most of the nonprotic ILs are synthesised by transferring an alkyl group to the basic
nitrogen site through SN2 reactions. Protic ILs are formed through
direct proton transfer from a Brnsted acid to a base (or a Brnsted
Scheme 7. Protic ILs synthesised by direct protonation (X = [NTf2], [CF3SO3], [CF3CO2], [CH3SO3], [HCOO], [HSO4], [H2PO3]).
Fig. 3. ILs based dendrimer polymers base (reprinted with permission from [95]. Copyright 2009 American Chemical Society).
ILs, either on the cation, either on the anion (Scheme 11). By adding
CO2 pressure to the solutions, the basicity can be signicantly
reduced. The basicity can be repeatedly recovered by removing CO2
by bubbling N2 to the ILs. This simple and reversible method could
have potential applications in different elds [113]. Further, some
basic ILs containing biodegradable components, including ILs
derived from natural amino acids have been developed [113].
Finally, ILs synthesised by the reaction of [RMI][OH] with
different poly-acids such as oxalic acid, malic acid, phthalic acid,
tartaric acid. can be mentioned. According to the quantity of acid
added, these ILs can display a certain acidity level. They have been
used as buffers in pH sensitive catalytic reaction for controlling the
acidity in non-aqueous media. The interest is that they may
present solubilisation properties in organic solvents [114].
In the case of these acid or basic ILs, it is worth emphasising that
the presence of impurities, such as water, halide, organic bases or
acids or traces of solvents, mainly coming from the synthesis of the
10
Scheme 12. Functional ILs as ligands and supports for transition metal complexes.
11
12
Table 2
Examples of deep eutectic solvents.
Compound 1
Compound 2
Carboxylic acids
Li+ NTf2
Acetamide
Li+ NTf2
Selected characteristics
Ref
[124]
[125]
[79]
[126]
[127]
[128]
13
Scheme 18. General route for ILs synthesis: (path A) metathetic exchange of anion, (path B) neutralisation of base with Brnsted acids, (path C) direct alkylation of
alkylimidazole, (path D) the carbonate method.
14
Scheme 20. Schematic representation of the different type of interactions present in imidazolium-based ILs.
Fig. 4. Normalised solvent polarity scale (ET(30) = 0.00 for Me4Si and ET(30) = 1.00 for H2O)reproduced by permission of The Royal Society of Chemistry [58].
15
Scheme 21. Possible location of the anions (represented as dotted circles) with
respect of the [RMI] imidazolium cation.
example [166]. The [BMI] cation forms stronger H-bonds than the
phosphonium cation with [Cl] as demonstrated by the exotherm
of mixing imidazolium and phosphonium ILs [167].
The strength of anioncation interaction inside the ILs
([RMI]+ + [A] $ [RMI][A]) has been investigated by ESI-MS (by
the abundance of fragments originating from C A C, with cation
named C and anion named A). Two classes of ILs have been
proposed: those with tightly associated anion to the 1,3-dialkylimidazolium cation such as: [CF3COO], [Br], [N(CN)2] and [BF4]
and those in which the anion is loosely interacting with the
imidazolium cation such as [OTf], [PF6], [NTf2]. Among the ILs
investigated, [NTf2] is the least interacting [168]. The weak [BMI]+
and [NTf2] interaction may have an important impact on metal
solvation. 1,3-Dialkylimidazolium [NTf2] ILs may be the solvents of
choice in catalytic systems that involve a chloride dissociation step
while being less solvating than water. For example, the ionic
strength of interaction has also been estimated by ab initio
calculation of the dissociative energies of different [BMI]+ or
[EMI]+ anion ion-pairs. For the [BMI]+ cation, it decreases in the
order [Cl] > [BF4] > [NTf2]. For the [EMI]+ cation, the intermolecular interaction energies of nine ion-pairs were studied.
The calculated interaction energies follow the trend
[CF3CO2] > [BF4] > [CF3SO3] > [NTf2] [PF6] (energies lie
between 78.4 and 89.8 kcal/mol) and the ectrostatic interaction
is mainly responsible of the attraction. For the [BF4] anion, the
interaction energies with pyrrolidinium or ammonium cation is not
signicantly different, demonstrating that the hydrogen bond with
C(2) of the imidazolium cation is not essential for the attraction.
Comparison with experimental ion conductivities show that the
magnitude and directionality of the interaction energy between ions
play also a crucial role in the dissociation and association dynamics
in ILs [49,169]. We have seen that for ILs containing the [EMI]+
cation, one of the strongest interactions is the CH anion
interaction via the proton in position 2. An interesting simple
way to determine the strength of this interaction is by 1H NMR
measurements. To exclude disturbing inuences on the ionion
interactions, all measurements must be carried out in neat ILs, in the
absence of other deuterated solvents. The 1H and 13C NMR shifts
obtained in that way show a good correlation with the calculated
ion-pair stabilisation energies (Fig. 5).
It has been shown that the presence of a co-solvent can
change the ion-pair strength. PGSE (Pulsed-Gradient Spin-Echo)
diffusion and HOESY NMR techniques have been applied for
studying inter-ionic interactions in ILs. For neat ILs such as
[BMI][BF4] and [BMI][NTf2], the diffusion constants, D-coefcient
values, are quite similar for the anion and the cation of the same
IL, and relatively small, but different for [BF4] and [NTf2] ILs.
Addition of methanol, as a co-solvent, results in an increase of the
D-values (also due to decreasing viscosity) up to a maximum
which may correspond to the completely solvated salt. The
methanol tends to separate the ions. On the contrary, in
dichloromethane, the anions and cations show strong HOESY
contacts which suggests that the cation and the anion form
strong ion-pairs in this solvent [171].
16
Fig. 5. Correlation between calculated ion-pair stabilisation energies and NMR-shifts for the proton and carbon at the C-2 position (reprinted with permission from [170].
Copyright 2009, American Chemical Society).
Scheme 22. Enantioselective hydrogenation of N-(30 -oxobutyl)-N-methylimidazolium (R)-camphorsulfonate. Effect of ion-pair interactions in the IL.
The most surprising effect of ion-pairing is probably demonstrated by the transfer of chirality in Michael type reaction
(Scheme 22). The hydrogenation of N-(30 -oxobutyl)-N-methylimidazolium (R)-camphorsulfonate using heterogeneous Ru on
charcoal in ethanol at 60 8C and 60 bar of hydrogen gives the
hydroxybutyl derivative with quantitative yield and enantioselectivities up to 80% ee. The correlation between the imidazolium
concentration and the enantioselectivity highlights the importance of ion-pair interactions. This chirality transfer approach can
be interesting, taking into account the large possibilities of
attaching substrates on imidazolium cations [172].
3.3. Toward a mesoscopic organisation
An understanding of the nano-structural organisation and
inter-ionic interactions of ILs is also crucial to understand their
solvent effect. The interaction of ILs with reactants, products,
activated molecules or complexes is another important concern
that needs to be taken into account to understand the solvent effect
on the outcome of the reaction. Different experimental and
theoretical methods have been reported to try to describe these
interactions. Three-dimensional supramolecular polymeric networks of cations and anions connected by H-bonds have been
several times evidenced (X-ray diffraction, NMR, neutron diffraction) (Scheme 23) [173,174]. The ability of ILs to give supramolecules has also been suggested by gas phase mass spectroscopy
experiments.
It is now proposed that ILs present supramolecular structural
organisation. Experimental and theoretical methods tend to
Scheme 23. Representative scheme of extended three-dimensional network of Hbonds in [EMI][Cl] ionic liquid.
that are formed by the head groups of cations and anions and nonpolar domains that are formed by alkyl chains on the imidazolium
cations. It can be seen as if the liquid structure of IL has large
cavities. The behaviour of ILs in viscosity, diffusion coefcient, and
ionic conductivity, can now be attributed to the presence of
microdomains, specially the break in the trends observed for
alkylmethylimidazolium cation having alkyl chain longer than
butyl [182]. The heterogeneity of the ILs can also explain their dual
behaviour when they are used as stationary phases for gas
chromatography (they can separate polar and as well as non polar
alkane compounds) [183]. The question now is: could the structure
of ILs affect catalytic reactions? should channels favour diffusion of
small molecules? This will be discussed in section 4. But, there is
still few data available in the literature.
3.4. Solute-ILs interactions: what impact on organic reactions?
Many studies have focused on the cationanion interactions
(solventsolvent interactions) rather than ionssolute interactions
(solventsolute interactions or solvent solvation). In conventional
medium, solventsolute interactions are generally predominant
while in ILs, interactions inside the solvent can become more
important. The Diels-Alder reaction is an interesting example
because it is a key step in many syntheses used to prepare cyclic
structures, and because the reaction performances in term reaction
rate and selectivity have been widely studied and are highly
solvent dependent. In the case of the reaction of cyclopentadiene
17
18
Table 3
Quantitative kinetic studies of nucleophilic SN2 substitution reactions of [Br] with
methyl p-nitrobenzenesulfonate [188].
[BMI][NTf2]
[BMP][NTf2]
CH2Cl2
k (M1 s1)
p*
0.0195
0.0296
0.460
0.617
0.427
0.042
0.243
0.252
0.014
0.984
0.954
0.791
Scheme 25. Reaction of chloride ions with ionic sulfonium electrophile (A = NTf2 or TfO).
toluene is located closer to the methyl group at the end of the butyl
chain, whereas in the case of [BMMI]+ cation, toluene was closer to
C(2)-Me of the imidazolium. The H-bonding association between
[BMI]+ and the [NTf2] is too strong to be cleaved by toluene. In the
case of C(2)-Me cation, the less strongly bonded IL network renders
possible the penetration and interaction of toluene [204].
3.4.3. Interaction with chiral substrates: induction of chirality?
Some Chiral ILs have been designed and synthesised, they have
already been applied in different elds such as asymmetric synthesis
(see reviews), stereoselective polymerization, chiral chromatography, liquid crystals, chiral resolution and as NMR shift reagents.
Chiral solvents have been reported in asymmetric syntheses.
However, low enantioselectivities are most of time obtained. In
the Baylis-Hillman reaction of benzaldehyde and methyl acrylate in
presence of a base, chiral ILs (Scheme 26) demonstrate their ability in
the transfer of chirality, even if the enantiomeric excesses are still
moderate. The presence of an alcohol function on the N-alkyl-Nmethylephedrinium is primordial and acts as a xing point of the CIL
on the reactants. It is indeed assumed that the OH group is connected
with a carbonyl function of the substrate (from either benzaldehyde
or methyl acrylate) via H-bonding. However, with N-methylephedrine, very low ee are obtained which also shows that the
ammonium group plays a crucial role in the chirality induction.
Even if not directly demonstrated, it seems that the key of effective
asymmetric induction is the existence of both strong intermolecular
interactions, like electrostatic attraction and hydrogen bonding,
between ionic solvents and intermediates or transition states of the
diastereoselective reaction step. The need of H-bonding in the
transfer of chirality has also been conrmed in the case of borate
based CIL bearing maleic acid functions. In this latter case, by
incorporating the acidic centre into the chiral anion of the solvent,
the IL offers the possibility of establishing a bifunctional interaction,
which allows monofunctional achiral nucleophiles to be used as
catalysts [205].
3.4.4. Interaction with acid and base: toward new scale of acidobasicity
The interest of ILs as solvents to perform acidbase reactions
has been recently increasing. A simple way to generate and
modulate the acidity is to add a Brnsted acid into the ionic liquid.
In that case a new scale of acidity can be obtained either by varying
the acid concentration in the IL or by changing the nature of the
ionic liquid [206]. If quite a lot of acid-catalysed reactions have
been reported in ILs, very few studies have been devoted to the
quantication of the acidity level of the proton in these media.
Nevertheless, as the acidity of protons is mainly determined by
their solvation state, the properties of protons will depend strongly
on the nature of the IL and the nature and concentration of the acid.
A rst apparent relative estimation of the proton acidity level has
been reported using the determination of the Hammett acidity
functions, by UVvis spectroscopy [207]. For a similar content of
added strong acid, the anion of ILs plays a fundamental role; the
acidity levels are in the order: [PF6] > [BF4] > [NTf2] > [OTf]
thus implying that the solvating power (or basicity) of the anions
follows the reverse order. The presence of basic impurities in the
19
ILs can also have a dramatic effect. Even if absolute acidities cannot
be determined with this method, global acidity must be (much)
higher than that observed in water.
3.5. Molecular modelling
Because of the potential number of cationanion combinations,
experimental investigations of all ILs properties are very difcult,
quite impossible. A molecular-based understanding of their
properties is important for their rational use. If molecular
dynamics (MD) calculations have been developed for inorganic
melts, liquid salts based on organic ions were not so extensively
explored. ILs are indeed not simple uids. The unusual complexity
of intra and intermolecular interactions in ILs renders interpretations very difcult and gives rise to controversies speculations.
Computer simulations have played an important role in the
prediction of physico-chemical properties of ILs starting from the
molecular structure of ions. The structure-properties relationship,
called QSPR (Quantitative Structure-Property Relationship), drives
most of theoretical studies. Many properties, useful for catalytic
applications, have been predicted requiring a combination of
several theoretical models and approaches (IL melting point [208];
solubility and partition coefcient of organic solutes in ILs [209];
viscosity [210]; surface tension [211]; ionic conductivity [49].
Cationanion interactions can be obtained using quantum
chemical calculations in gas phase. This calculation gives details on
ion-pair stability, intramolecular geometry, and orientation of ions
in the pair and allows a better understanding of H-bonds and
charge transfer between ions. One limitation is the size of
dialkylimidazolium cations. Different correlations could be
obtained between the energy of ion pairs (ion-pair association
energy) and the different structure of ILs and their melting points
[212]. Based on DFT calculations, the high viscosity and the low
pressure of ILs could be rationalized with the location of the anion
and the possible H-bonds with the dialkylimidazolium cation. The
transport properties in the liquid are affected by the presence of
the anion which inuences the barrier for rotation of the alkyl (e.g
butyl) present on the imidazolium cation.
Ab initio techniques raise some issues: the poor performance of
DFT in dealing with systems bearing delocalized charge; the
problem associated with the calculation of a meaningful charge
on each atom in a delocalized molecular ion. Ab initio molecular
dynamics, which combines electronic structure calculations with
conventional MD (called AIMD), is the only technique able to predict
the intermolecular structure of ILs (under specic thermodynamic
conditions). However, a major limitation of such simulation is the
length and time scale that can reasonably be explored and the need
for extensive computational resources. Long range organisation of
ILs cannot easily be explored with this method. These studies have
essentially been performed on dialkylimidazolium associated with
halide or [PF6] anions. They clearly identify the existence of H-bond
between C(2)-H and the chloride anion [213]. The signicance of the
simulation crucially depends on the quality of molecular force eld
used. Different groups tried to develop and rene force elds for ILs
[214]. The growth of computational studies in ILs was driven by the
development of force elds for a wide variety of ILs [215]. The
Scheme 26. Baylis-Hillman in N-alkyl-N-methylephedrinium. First example of transfer of chirality. Because of the strong interactions between the IL and the reactants
enantiomeric excess have been obtained.
20
interaction of the chloride anion with the 1-butyl-3-methylimidazolium has been estimated by variable-temperature 1H NMR
measurements (Scheme 27).
In [BMI][OTf], the solvation enthalpy of the chloride
[DHsolv = 46.2 kJ/mol], is about eight times lower than the
solvation enthalpy of chloride in water. The strong coordination
ability of the chloride anion in 1-butyl-3-methylimidazolium ILs
can be related to the low solvation enthalpy of chloride in such
ionic liquids (the energy of interaction of the chloride with [BMI]+
is relatively weak: 15 kJ/mol). This can explain that chloride
dissociation from a transition-metal complex can be thermodynamically disfavoured in ionic liquids and might be inhibited in
these solvents. An example is given by the catalytic activity of
cationic ruthenium(II)-arene diphosphine complexes in different
ILs systems compared to water [230]. In ILs, without any water, the
Ru(II) precatalyst is inactive. Addition of water to the IL
([BMI][OTf]:H2O 50:50) results in activation of the Ru complex
and formation of an active hydride species (Scheme 28). This
example shows the crucial role that water can play in facilitating
the solvation of the dissociated chloride.
Now in neat and dried ILs, the activation of the ruthenium(II)
catalyst precursor occurs via an unexpected mechanism, which is
different from the activation mechanism that takes place as
previously described in water or in water-ILs for the same reaction
[231]. Both the cation and the anion of the IL display an important
effect (promotor or inhibitor) on the rate of styrene hydrogenation
which can be correlated with the differences in capability of the IL
to solvate chloride.
4.1.3. Effect of bases
A key step in the synthesis of most ILs is the alkylation of 1methylimidazole with the corresponding 1-haloalkane. ILs have
21
Scheme 28. Proposed mechanism of formation of the Ru active species for the hydrogenation of arene in water and in presence of ILs.
22
23
Scheme 32.
24
Scheme 35. Oxidative addition of the imidazolium IL to Ni(0). Mechanism of catalyst deactivation.
catalysed by Ni(0) in [BMI]+ based ILs, active cationic [(carbene)Ni(II)-H]+ catalyst can be generated without any added coactivator by the direct oxidative addition of the [BMI]+ to the
Ni(0). But deactivation occurs rapidly after insertion of ethylene by
a reductive elimination process leading to the formation of 2alkylated imidazolium salt (Scheme 35).
A direct synthesis of NHC-iridium from neat IL has been also
recently reported [266]. The 1,3-dialkylimidazolium halides ILs
inhibit the methoxycarbonylation of iodobenzene with all Pd
precursors used. However with C(2) substituted dialkylimidazolium chloride, the reaction proceeds in a similar way than in [BMI]+
based ILs containing the weaker coordinating anions [BF4] or
[PF6]. A deactivation process has been proposed which involves
the formation either of a Pd(bis-carbene) with phosphine free Pd
precursors, or the formation of a phosphonium salt if phosphines
are present with the Pd precursors used [253]. The formation of
[BMI]2[PdCl4] salts in [BMI][Cl] or Pd(bis-carbene) can also prevent
the nanoparticles to growth and limit activity for CC Heck
coupling reactions. Other evidence of carbene formation is during
the synthesis of nanoparticles of Ir(0) from [Ir(1,5COD)(CH3CN)2][BF4] under D2 and in presence of [BMI][NTf2],
acetone and proton sponge. H/D labelling and 2H NMR reveal the
formation of N-heterocyclic carbene and its coordination with the
Ir(0) nanoparticles [267]. D/H exchange reactions at the imidazolium-d3 cation (80% at the C(2) position and 4% at the C(4) and C(5)
have also been observed in hydroformylation reactions of 1-octene
catalysed by Rh(acac)(CO)2(xantphos phosphine ligand) in
[BMI][NTf2] at 75 8C and under 5 atm of CO/H2. This result
suggests the in situ formation of heterocyclic carbenes. Both
hydroformylation and H/D exchange are catalysed essentially by
25
Scheme 37. Side reaction of the [BMI]+ cation with the aldehyde in presence of DABCO base.
26
the nature of the counter anion of the catalyst salt. The reaction
could give the N-tosyldihydropyrole 2 together with the cycloisomerisation and isomerisation by-products 3 and 4 (Scheme 41).
Therefore the catalytic transformation of the diallyltosylamine
was
investigated
with
complexes
[(p-cymene)RuCl(PCy3)5
5C5
5C5
5CPh2][X] in which the anion was varied (X = [PF6],
[BF4], [OTf]) in different [BMI]+ based ILs. One of the rst
questions that was asked when investigating catalysis in ILs was: is
the species that is actually present in ILs the same as the one that
was originally used. These experiments demonstrate that the
catalytic RCM transformation depends on the nature of the counter
anion of both the catalyst and the IL. This suggests that an anion
exchange rapidly takes place and that the catalytic system involves
the anion of the ionic liquid used rather than that of the initial
ruthenium precursor. It was found that the [BMI][OTf] IL affords
the best results in selectivity for 2 as it was the case with triate
ruthenium complex using toluene solvent [278].
To understand the ILs effect, investigations were performed on
the model process of ligand susbtitution on a well-known Pt(II)
complex in ILs, the entering molecule being thiourea named TU
(Scheme 42). The reaction was followed using UV/vis spectroscopy.
In general, as there is an increase in dipole moment in going from
the reactant to the transition state, a decrease in solvent polarity
results in a decrease in the rate of the reaction. In general ILs, the
substitution mechanism was found to follow an associative
substitution similar to that in conventional organic solvents.
However, ILs have a signicant inuence on the course of
Scheme 42. Competing coordination to the Pt centre between thiourea and IL anion
(TU = thiourea and ppp = terpyridine).
27
Scheme 43. Examples of hydroxyl-functionalised ILs used to solubilise PVP and stabilise Rh-nanoparticles.
28
bond by H bonding with the X atom and could aid in the solvation
of the salts generated during the reaction, thereby preventing
catalyst poisoning [298].
Table 4
Some examples of concepts developed for sulfur removal from hydrocarbon
streams.
Concept
Added
reactant
Type of ILs
Ref.
Photochemical oxidation
Oxidative desulfurisation
Extractive desulfurisation
H2O2
H2O2
No
[308]
[309]
[310]
Extractive desulfurisation
Alkylation of sulfur
derivative
No
Alkylating
agent
[BMI][PF6]
Protic IL, [MI][BF4]
Phosphoric acidfunctionalised ILs
Fe-containing ILs
Non-cloroaluminate
[311]
[312]
29
30
31
Fig. 11. Supported Ionic Liquid Phase (SILP) catalysis concept for olen hydroformylation. The IL is conned on the surface of silica through covalent anchoring (reprinted with
permission from [337]. Copyright 2009 American Chemical Society).
32
Fig. 12. Schematic representation of SILP: the IL is conned on the solid support by
physisorption (example of the MeOH carbonylation)reproduced from [343] by
permission of The Royal Society of chemistry.
length, the loading level of the IL portion and the nature of the IL
anion (Fig. 13). The catalytic properties of this new material were
examined through the study of nucleophilic uorination and
bromination of 2-(3-methanesulfonyloxypropyl)naphthalene as a
model compound. Best results were obtained with the PSIL
(Polystyrene supported ionic liquids) presenting the longest linker
(hexyl or dodecyl) with BF4 as counteranion. The desired
uoroalkane and bromoalkane were produced almost quantitatively. The effect of the PSIL loading (mmol of IL per gram of PS
resin) was also investigated. It appeared that large PSIL loading
produces the best result for uorination reaction (matrix effect)
whereas for bromination reaction, the reverse tendency is
observed (both matrix and site isolation effects). Interestingly,
no reaction occurred when PS with no IL portion is used.
Poly(ethylene glycol) (PEG) polymers have received rising
interest as a reusable solvent medium for organic synthesis and
catalytic process. The combination of PEG with ILs was realised by
the synthesis of PEG-functionalised ILs. These ILs have proved to
display interesting chemical and physical properties [348]. Their
application in catalysis is not very developed but may offer
interesting opportunities [349]. PEG-supported ILs have also been
shown to be efcient media for catalytic reactions such as CC
coupling with Pd(OAc)2, thus providing a ligandless recyclable
system [350].
5.3. Switchable polarity solvents
Some specially-designed solvents may reversibly switch their
polarity from a low polarity form to a higher polarity form when a
trigger is applied. In this concept, the modication of the solvent
polarity induces solubility changes of products and/or catalysts,
making their separation and purication feasible. For the concept
of switchable solvents, the polarity change is performed by
addition of CO2 to a mixture of two liquid components, either
amidines and an alcohol [351] or primary amine/amidine mixture
[352] or secondary amines (without amidines) [120]. In both cases
a carbamate salt forms which can then be assumed as an ionic
liquid (Fig. 14).
This concept has been applied recently as a post-treatment step
in the alternating polymerization of cyclohexene oxide with CO2
[120]. The polymerization reaction is performed using [PPN]-N3 as
co-catalyst and Cr(salen)Cl as catalyst under 35 bar of CO2 without
solvent (Scheme 44). After the polymerization section, the CO2 was
released and the polymer and the catalyst dissolved in the NHEtBu.
When CO2 is bubbled through this new mixture, the secondary
amine is converted into the polar carbamate salts in which the
polymer precipitates. The colour of the solution indicates that the
catalyst remains mainly in the solution. Slight colouration of the
polymer is nevertheless observed but can be corrected by several
SPS cycles. Remarkably, the chromium catalyst can be recovered by
distillation of CO2 and the amine, and nally reused for
polymerization.
33
In an equivalent approach, Jessop et al. reported the polymerization of styrene using DBU and 1-propanol as the SPS system
[121]. In that case, CO2 and N2 at 1 bar were used as polymer
miscibility and immiscibility triggering agents (Fig. 15). Interestingly, the molar ratio of DBU and 1-propanol was 1:2.5, the excess
of 1-propanol reducing the viscosity of the polar form (75 7 cP)
which then facilitates ltration of the polymer. This solvent can be
used several times (4 cycles) with nevertheless the need for fresh
solvent addition in order to compensate losses during ltration.
Recently a new class of one-component, thermally reversible,
neutral to ionic liquid solvents were described [353]. Its structure
is based on siloxylated amines which introduce weak Lewis acid
34
Scheme 47. Thermoregulated ionic liquid catalytic process for olen hydroformylation.
35
Fig. 17. Mass transfer model for epoxidation in [BMI][PF6]/water PTC system (Q+ = dialkylimidazolium cation; M = sodium; X = hexauorophosphate anion).
36
AlCl3
(1)
(2)
(3)
Fig. 19. Dimersol + Difasol package reaction: (1) Dimersol reactor(s), (2)
Vaporisationcondensation, (3) Difasol reactor.
37
38
Table 5
Ionikylation pilot plant alkylate vs HF and H2SO4 processesa.
Yield (wt%)
Process
HF
H2SO4
C5
C6
C7
C8
C9+
0.6
1.0
2.0
95.6
0.8
2.5
1.9
2.9
90.1
2.6
8.8
4.9
3.9
80.7
5.7
C8 components
TMPs
2,2,3-TMP
2,2,4-TMP
2,3,3-TMP
2,3,4-TMP
89.6
0.1
51.6
18.1
19.8
80.9
1.6
49.7
10.8
18.8
71.6
2.3
31.1
19.8
18.4
6.0
1.3
3.4
1.3
0
9.2
9.0
14.9
100.1
95.0
8.8
97.3
95.2
8.0
97.6
94.4
Ionikylation
DMHs
2,3-DMH
2,4-DMH
2,5-DMH
3,4-DMH
TMP:DMH ratio
RON
MON
a
at room temperature and provides good quality alkylate (2,3dimethylbutane is the major product) over a period of 300 h
(MON = 9094; MON = 98101). When butenes are used instead of
ethylene, a lower temperature and a ne tuning of the ILs acidity
are required to avoid cracking reactions and heavy by-product
formation. The continuous butene alkylation has been performed
for more than 500 h with no loss of activity and stable selectivity
(8090% isooctanes are obtained containing more than 90%
trimethylpentanes TMP; MON = 9095; RON = 9598). At that
time, it had been demonstrated that the addition of copper(I)chloride to the acidic chloroaluminate improves the reaction
performance [388]. Some years later, Petrochina developed a
process called Ionikylation for the alkylation reaction [389]. The
ionic liquid used consists of a mixture of a conventional
chloroaluminate-IL with CuCl. In this composite IL, large quantities
of mixed anion like AlCl4CuCl were detected [390]. It is theorised
Table 6
Alkylate from commercial H2SO4 unit before and after retrota.
H2SO4 alkylation
Ionikylation
Yield (wt%)
Yield (wt%)
Feed
C4
180
248
Product
Light alkylate
Heavy alkylate
Gas
Loss
Total
125.9
10.8
41.7
1.4
180
70.0
6.0
23.2
0.8
100
186.1
8.2
53.7
248
75.0
3.3
21.7
100
RON
MON
AntiKnock index
95.0
93.0
94.0
98.8
93.1
96.0
45.0
77.0
101.5
108.5
132.0
45.5
81.5
101.0
108.0
154.0
0.9
Pass
1
1.6
Pass
1
Octane rating
Distillation (8C)
39
40
forms a second lower phase with the pure product in the upper one
giving feasible the separation of products by simple decantation
[396398]. Interestingly, the 1-methyl-imidazolium chloride
[MI][Cl] co-produced in the reaction can be treated with caustic
soda to regenerate 1-methylimidazole.
In this work, 1-methylimidazole was also identied as a
nucleophilic catalyst. When used, it led to consirable improvement
of the phosphorylation rate. Taking this effect into account, BASF
developed a specic reactor technology (jet reactor) which
increases productivity by a factor of 80,000. The role of 1methylimidazole as acid scavenging was further extended to other
similar problems and revealed to be also very efcient [365]. The
BASILTM process is actually applied by BASF at a multi-ton scale.
6.1.7. Hydrosilylation: IL as solvent and nanoparticle stabiliser
Organomodied siloxanes account for approximately 15% of the
entire silicone market and are accessible in a number of ways
[399], including the catalysed hydrosilylation of C5
5C double bond
containing compounds with Si-H-functional polydimethylsiloxanes (Scheme 54). Particularly interesting are polyethersiloxanes,
constituting an important class of surface-active compounds
which nd use in a broad range of industrial applications.
The hydrosilylation reaction is usually performed in a singlephase homogeneous system with, nevertheless the recurrent
problem of catalyst and product separation after completion of
the reaction. To overcome this limitation, Degussa introduced the
use of ionic liquid as a way of catalyst heterogenisation
[331,400,401]. This work was directed by the need for using the
standard platinum catalyst without modication. Several ionic and
neutral catalysts as well as ionic liquids were then evaluated. As an
important parameter of the study the separation behaviour of the
ionic liquid and the product were particularly studied. It turned out
that for successful recovery of the catalyst and its reusability it is
crucial to nd an appropriate combination of a catalyst and an ionic
liquid which has to be harmonised with the hydrophilicity/hydrophobicity of the product. For example of this ne tuning, it was
demonstrated that hydrosilylation with ILs derived from 1,3dialkylimidazolium salts did not give the desired polyethersiloxanes. The authors assumed that formation of NHC-carbenes which
coordinate to the Pt centre is responsible of the catalyst deactivation.
41
Table 7
Other examples of industrial/pilot scale applications of ILs.
Company
Scale
Ionic liquid
Role of the IL
Ref.
BASF
Pilot
[RMI][BF4]
[406,407]
Air products
Commercial
[RMI][BF4] [RMI][Cu2Cl3]
[RMI][Cu2Br3]
Scionix
Scionix
Pilot (1200 L)
Pilot (50 L)
[HO(CH2)2NMe3][Cl]
Electrolyte
Electrolyte
[410]
[79,125]
G24i
Commercial
Electrolyte
[411,412]
Engineering uids
Hydraulic liquids
Cleaning uids
Linde
Iolitec/Wandres
Pilot
Pilot
Liquid piston
Cleaning agent
[413415]
[365]
Analytical chemistry
Commercial GC-stationary phase
Supelco
Commercial
[1,9-di (3-vinyl-imidazolium)
nonane] [NTf2]
GC-stationary phase
[416]
Separation/storage
EtOH/H2O or EtOH/THF separation
Storage of gases
Electrochemistry
Electroplating of Cr
Electropolishing of stainless steel
Energy
Dye Sensitized Solar Cells
(DSSCs or Gratzel cells)
[408,409]
42
43
Fig. 20. The cellulose network (A: Cellulose chain and B: inter and intra H-bonds present in cellulose).
Table 8
Main solvent systems used in manufacturing cellulose and cellulose derivatives
[434].
Acronym
DMSO/TBAF
LiCl/DMAc
LiCl/DMI
LiCl/NMP
N2O4/DMF
DMSO/CH2O
NMMO
44
Table 9
Examples of solubility of different bio-products in ILs and organic solvents.
Solvent
Solubility
Glucose
substrate
DP (cellulose)
2-Methyl-2-propanol
[BMI][N(CN)2]
[BMI][Cl]
0.03 (wt%)
145 (g/L)
50 (g/L)
Sucrose
Sucrose
Sucrose
Sucrose
Sucrose
Acetone
Pyridine
[BMI][Cl]
[BMI][Cl]
[BMMI][Cl]
[BMI][Cl]
[BMI][Cl]
[BMI][Cl]
[BMI][Cl]
[BMI][Cl]
[BMI][Cl]
[BMI][Cl]
Cellulose
Cellulose
Cellulose
Cellulose
Cellulose
Cellulose
Cellulose
286
593
1000
1000
1000
1198
6500
Cellulose
225
Cellulose
T (8C)
Ref.
25
25
70
[444]
[444]
[445]
0.007 (wt%)
6.45 (wt%)
5 (wt%)
18 (wt%)
14 (wt%)
30
26
70
110
120
[430]
[430]
[445]
[446]
[446]
18
13
3
10
25
10
6
83
83
70
100
110
83
80
[447]
[447]
[436]
[436]
[436]
[447]
[448]
(wt%)
(wt%)
(wt%)
(wt%)
(wt%)a
(wt%)
(wt%)
[BMI][Fm]
8 (wt%)
110
[441]
250
286
593
1198
[BMMI][Cl]
[BMI][Cl]
[BMI][Cl]
[BMI][Cl]
4.5 (wt %)
9 (wt%)
6 (wt%)
4 (wt%)
110
80
80
80
[446]
[449]
[449]
[449]
Cellulose
650
1600
[AMI][Cl]
[AMI][Cl]
14.5 (wt%)
8 (wt%)
80
80
[450]
[451]
Cellulose
286
593
1198
[AMMI][Br]
[AMMI][Br]
[AMMI][Br]
12 (wt%)
4 (wt%)
4 (wt%)
80
80
80
[449]
[449]
[449]
Cellulose
250
250
[AMI][Fm]
[AMI][Fm]
10 (wt%)
22 (wt%)
60
85
[77]
[77]
Cellulose
286
593
1198
[EMI][Cl]
[EMI][Cl]
[EMI][Cl]
12 (wt %)
6 (wt %)
4 (wt%)
80
80
80
[449]
[449]
[449]
Cellulose
Cellulose
Cellulose
Cellulose
Cellulose
Cellulose
795
200250
200250
200250
200250
200250
[EMI][Ac]
[EMI][PO2(H)(OMe)]
[EMI][PO2(Me)(OMe)]
[EMI][PO2(OMe)2]
[EMI][PO2(OEt)2]
[MMI][PO2(OMe)2]
20
10
10
10
14
10
80
45
55
65
100
100
[439]
[451]
[451]
[451]
[437]
[437]
Cellulose
286
593
1198
[BMPy][Cl]
[BMPy][Cl]
[BMPy][Cl]
39 (wt%)
37 (wt %)
12 (wt %)
105
105
105
[447]
[447]
[447]
Cellulose
200250
6.8 (wt%)
70
[452]
9.7 (wt%)
13.9 (g/L)
110
75
[446]
[453]
50
50
[453]
[453]
130
[454]
85
85
85
85
[455]
[455]
[455]
[455]
80
[456]
[(HO(CH2)2)MI][Cl]
(wt%)
(wt%)
(wt%)
(wt%)
(wt%)
(wt%)
Lignin
[BMI][Cl]
[BMI][Cl]
Lignin
Lignin
[MMI][MeSO4]
[BMI][MeSO4]
[BMI][Cl]
11 (wt%)
[EMI][Ac]
[EMI][Cl]
[BMI][Ac]
[BMI][Cl]
13.5
15.8
13.2
13.6
[BMI][N(CN)2]
15 (wt%)
Eucalyptus
Eucalyptus
Eucalyptus
Eucalyptus
pulp
pulp
pulp
pulp
Starch
a
Microwaves heating.
569
569
569
569
344 (g/L)
312 (g/L)
(wt%)
(wt%)
(wt%)
(wt%)
45
46
Table 10
Some parameters to consider regarding the solubility of bio-polymers in ILs.
IL cation
IL anion
Mp (8C)
Viscosity
mPa s (at RT)
Solvato-chromic
parameter b*
[BMI]+
[AMI]+
[AEI]+
[AMI]+
[BMI]+
[BMI]+
[BMI]+
[BMI]+
[BMI]+
[Cl]
[Cl]
[Fm]
[Fm]
[Fm]
[NTf2]
[OTf]
[N(CN)2]
[PF6]
66
17
<20
76
11,000
2090
67
66
156
52
0.830.87
0.83
0.99
0.99
1.01
[BMI]+
[Ac]
[EMI]+
[EMI]+
[EMI]+
[EMI]+
[Ac]
[PO2(H)(OMe)]
[PO2(Me)(OMe)]
[PO2(OMe)2]
[EMI]+
[MeOSO3]
[MeSO3]
[BMPy]+
[Cl]
2
13
6
0.46
0.21
<20
86
66
74
646
1.09
140
107
510
265
1.00
1.07
1.00
0.61
0.70
Cellulose dissolution
95
the regenerated sample can have the same degree of polymerization and polydispersity, although this much depends on the
operating conditions of the treatment. Generally macro- and
micro-structure especially the degree of crystallinity can be
drastically changed and modulated by changing the conditions
of regeneration. For example, cellulose reconstituted after being
dissolved in [AMI][Cl] and [BMI][Cl] had lower degrees of
crystallinity than native cellulose [475]. It has been shown that
the resultant regenerated cellulose is mostly amorphous with
greater accessibility of the polysaccharide chains to cellulase and
exhibits improved enzymatic hydrolysis kinetics (Fig. 21)
[458,466,476].
7.1.2. Treatment of lignocellulosic materials
Lignocellulosic biomass (Fig. 22) which comprises cellulose
(3345%), hemicellulose (2030%) and lignin (1530%) is perceived
as a future valuable resource but separation, recovery and
processing of all its components in a cost-effective way represents
a signicant technical challenge. The effectiveness of lignocellulose
pre-treatment is one of the keys to successful conversion of this
originally low-cost material into sugars and by enzymatic or
catalytic hydrolysis into biofuels or biofuel intermediates.
A number of lignocellulose pre-treatments are being investigated either at lab scale or in pilot plants, including various
chemical, physical or physico-chemical approaches such as acidbased methods (dilute or concentrated sulphuric acid), steam pretreatments (steam explosion), solvent extraction methods (organosolv) or ammonia methods (ammonia bre explosion (AFEX),
ammonia recycle percolation (ARR)) [477]. Many of these
techniques suffer from relatively low sugar yields, high costs
and fractionation and isolation of the major components remains
uncompleted. All these pre-treatments have the main objective of
separating the cellulose for a future enzymatic conversion.
However limiting factors exist and hinder the accessibility to
the enzymes. Generally these factors are divided into two groups:
the biomass structural features, the so called biomass recalcitrants,
and the enzyme mechanism. While enzymatic hydrolysis solely
depends on the accessibility, the structural feature is more
complex [478].
Recalcitrances of lignocellulosic bio-materials to cellulase
enzymatic hydrolysis can be attributed to the accessible surface
area, crystallinity, the protective lignin, degree of polymerization
47
Choosing the appropriate pre-treatment for a biomass feedstock is often a compromise between minimizing degradation of
the hemicellulose and cellulose while maximising the ease of
enzymatic hydrolysis of cellulosic substrate.
Fig. 23. Example of wood chips dissolution in [EMI][Ac] as the ionic liquid
(reprinted from [438], Copyright 2009, with permission from Elsevier).
48
49
Table 11
Results of homogeneous cellulose acetylation in ILs (acetic anhydride is used as
reagent).
Ionic liquid
Reagent mol
per glucose unit
t (min)/T (8C)
Degree of
substitution
Ref.
DMAc/LiCl
[BMI][Cl]
[EMI][Cl]
[BMMI][Cl]
[AMI][Cl]
[AMI][Cl]
[EMI][Ac]
[EMI][Ac]
5
5
3
3
5
5
3
5
120/80
120/80
120/80
120/80
15/80
480/80
15/25
15/25
12.94
2.72
3
2.92
0.94
2.49
2.31
3.00
[504]
[447]
[449]
[449]
[505]
[505]
[443]
[443]
50
Table 12
Methanolysis of triglycerides using ILs.
Catalyst
Ionic liquid
Use
Remarks
Ref
Metal salts
[BMI][InCl4]
IL-catalyst
[512]
Organic base:
NaOMe, KOH, LDA. . .
[PR4][N(CN)2]
[509]
Tin compound
[BMI][PF6]
Three-phase system
[511]
Ester/water-glycerine/
IL-catalyst
Lewis acid
[BMI] based
chloroaluminate
IL-catalyst
[515]
Brnsted acid
Sulfonated imidazolium
Acid supported on
the BMI cation
[514]
[BMI][NTf2]/water
Biphasic system
Reuse of enzyme
[508]
51
52
53
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