Potential Applications of Deep Eutectic Solvents in Nanotechnology

Chemical Engineering Journal 273 (2015) 551567
Contents lists available at ScienceDirect
Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej
Review
Potential applications of deep eutectic solvents in nanotechnology

Ali Abo-Hamad a,b, Maan Hayyan a,c,, Mohammed AbdulHakim AlSaadi a,d, Mohd Ali Hashim a,b
a
University of Malaya Centre for Ionic Liquids (UMCiL), University of Malaya, Kuala Lumpur 50603, Malaysia
Department of Chemical Engineering, University of Malaya, Kuala Lumpur 50603, Malaysia
c
Department of Civil Engineering, University of Malaya, Kuala Lumpur 50603, Malaysia
d
Nanotechnology & Catalysis Research Centre (NANOCAT), University of Malaya, Kuala Lumpur 50603, Malaysia
b
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
DESs can play a primary role in
nanotechnology.
Up-to-date articles pertaining to DES
contribution in nanotechnology were

reviewed.
The most current DESs applications
are in chemical and electrochemical
synthesis.
The current vision foreshadowed an
entirely new areas of nanotech built
on DESs.
a r t i c l e
i n f o
Article history:
Received 30 October 2014
Received in revised form 28 February 2015
Accepted 9 March 2015
Available online 25 March 2015
Keywords:
Deep eutectic solvent
Ionic liquid
Nanomaterial
Carbon nanotube
Electrodeposition
Dispersion
a b s t r a c t
Deep eutectic solvents (DESs) have recently received a great interest in diverse elds including nanotechnology due to their unique properties as new green solvents, efcient dispersants and as large-scale
media for chemical and electrochemical synthesis of advanced functional nanomaterials. DESs have also
an active role in improving the size and morphology of nanomaterials during synthesis stage. Moreover,
DESs conned in nano-size pores or tubes show distinct behavior from those in the same types but in
larger scales. Therefore, a numerous studies sprung up to expose the importance of the synergy between
DESs and nanomaterials. This review revealed the recent studies that devoted to the impact of involving
DESs in nanotechnology and potential applications.
2015 Elsevier B.V. All rights reserved.
Contents
1.
2.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1.
History of DESs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2.
DESs as analogs of ILs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3.
Properties of DESs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3.1.
Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3.2.
Solvation properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Main applications of DESs in nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Corresponding author at: Department of Civil Engineering, University of Malaya, Kuala Lumpur 50603, Malaysia. Tel./fax: +60 3 7967 5311.
E-mail address: maan_hayyan@yahoo.com (M. Hayyan).
http://dx.doi.org/10.1016/j.cej.2015.03.091
1385-8947/ 2015 Elsevier B.V. All rights reserved.
552
552
552
552
553
554
554
552
A. Abo-Hamad et al. / Chemical Engineering Journal 273 (2015) 551567
2.1.
3.
Media to disperse nanoparticles and control morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.1.1.
Dispersants for nanomaterials to form nanocomposites and nanofluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.2.
Media to split nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.3.
Media to obtain special sizes and morphologies of nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.4.
Electrolytes for electrochemical systems with nanostructured electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.5.
Media to produce efficient and recyclable nano-catalytic assembly . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Reaction media for nanomaterial production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1.
Solvents and reactants for the physicochemical synthesis of nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.2.
Electrolytes for nanomaterial electrodeposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.3.
Media for sputter deposition to produce nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.4.
DES-based nano production: an overview about applications, advantages and challenges. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.
Applications of nanosized DESs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
A DES is generally a combination of two or more components
which are able to associate with each other. The concept of DES
was rst introduced by Abbott et al. [1] as a mixture of two or more
components that forms a eutectic, the melting point of this eutectic
mixture is lower than both of the individual components. The most
popular component among all DESs is choline chloride (ChCl)
which is similar to B vitamins, and it is a biodegradable and nontoxic salt [1,2]. Over the last decade, there has been a rapid development in DESs as designer solvents for various applications [3].
Furthermore, DESs, as a new type of green solvent, have some
recognized properties, such as high viscosity, high thermal stability
and low vapor pressure [4].
1.1. History of DESs
A new solvent foundation was laid in 2003 reported by Abbott
et al. and dubbed deep eutectic solvents (DESs) [1]. This term
usually refers to a mixture of a halide salt and a hydrogen bond
donor (HBD) to produce liquid [5]. The rst appearance of DES
was as mixture of salt based on quaternary ammonium cation
and a hydrogen donor (amine, imides, and carboxylic compounds).
This eutectic phenomenon was rst introduced through a mixture
of urea and ChCl with a 2:1 molar ratio and melting points 133 C
and 302 C, respectively. The result was a eutectic mixture that
melts at 12 C [6]. Physicochemical properties for DESs are similar
to those of ILs, therefore, exploiting them attracted other researchers [7]. Copper(II) oxide and lithium chloride were successfully dissolved in this DES. Hence, DESs started to be used as solvents for
metal cleaning prior to electroplating. Later, DESs were also utilized as a medium for electrochemical deposition and different
metals were successfully electrodeposited such as Ag, Zn, Sn, Cr,
and Cu [8,9]
The increasing interest of DESs is attributed to their potential to
be even more environmentally benign compared to the earlier traditional ILs besides having almost similar solvation properties, putting forward many potential applications in different elds of
chemistry and electrochemistry. So far and due to economic reasons, the cases of using DESs at a commercial scale are still in nite
amounts [10].
1.2. DESs as analogs of ILs
ILs have been introduced as new alternative solvents to replace
conventional ones for the use in synthetic processes [11]. Having a
combination nature of cation and anion with at least one of them is
naturally organic and melts below some arbitrary temperatures is
what made them dened as molten salts [12]. However, based on
555
555
556
556
557
557
557
557
557
557
560
565
565
565
565
melting point range of ILs, they can be described either as room

temperature ILs when they melt at room temperature or as near
room temperature IL if they melt below 100 C. One of the key features that distinguish ILs form other competitive solvents is the
low vapor pressure comparably [13].
Recently, a special class of ILs was introduced and believed to be
a new generation of ILs which known as DESs. These solvents are
generally based on mixtures of quaternary ammonium or phosphonium salt and an uncharged hydrogen bond donor such as
amide, acid or alcohol with a much lower melting point than that
of any of its individual components have recently gained attention.
In literature, DESs are sometimes referred to analogs of ILs [14],
even though they could not be dened as true ILs as they are not
completely comprised of ionic species. The syntheses of these compounds proceed simply by mixing together two components
(cheap, renewable and biodegradable), which are able to form a
eutectic mixture. This does not include any additional solvent or
formation of by-products, and results in easily biodegradable products [15].
Regarding material synthesis eld, a comparison between the
ILs and DESs use shows rareness for DES cases because of their
recent appearance in the few past years. Nevertheless, seminal
work was reported in ionothermal synthesis for both solvents.
There are unlimited opportunities to prepare numerous DESs
because of the high exibility to choose their individual components as well as their composition. Thus, a plenty of room is available for the development of fundamental research in eld of DESs.
Different properties can be attained from DES production and
envisaged applications can be achieved especially in high-tech production and processes that demand low costing materials [13].
This review is to focus on nanotechnology side that has employed
DESs in the discovery of new routs of synthesis, improving the performance and following up with new ndings and applications.
Our hope is to encourage researchers to follow up deeply with
these aspects in order to spread the use of DESs among the world
and make it real in near future.
1.3. Properties of DESs
DESs are close to ILs regarding the fact of being adoptable in
numerous applications [16]. This can be achieved through the
proper combining between salts and HBDs. As a result, it is possible to design a task-specic DES that could meet the electrochemical or physicochemical properties required for certain area of
application. [17]. As they are able to dissolve some metal oxides
(MOs), DESs have opened the door for new interesting avenues in
chemistry in particular [18]. Solubility limitations are selected by
the HBD of the DES. A great interest of DESs as novel solvents are
also placed on the employment of electrochemical procedures to
553

Table 1
Some physicochemical properties for different types of DESs.
1st component
1st component
Tm/f (C)a
2nd component
2nd component
Tm/f (C)a
DES molar
ratio 1st:2nd
DES freezing
point (C)
Density
(g cm3)
Viscosity
(cP)
Surface tension
(mN m1)
Ref.
ChCl
ChCl
ChCl
ChCl
ChCl
302305
302305
302305
302305
302305
U
TU
1,3-DU
EG
G
132135
170176
101104
13
20
12
69
70
66.01
36.15
32.65
1.25
750 (25 C)
52
1.12
1.18
1.20
302305
302305
TFA
AA
7375
13
ChCl
MPB
MPB
MPB
302305
230234
230234
230234
ZC
G
EG
TEG
293
20
13
7
37 (25 C)
259 (25 C)
450 (20 C)
503 (20 C)
77 (40 C)
115 (22 C)
77 (22 C)
85000 (25 C)
48.91
ChCl
ChCl
1:2
1:2
1:2
1:2
1:2
1:3
1:4
1:2
1:1.6
1:2
1:2
1:3
1:4
1:5
[1,9597]
[1]
[1]
[5,98100]
[5,95,98100]
[5,98,100]
[100]
[96]
[101]
[101]
[102]
[98,99,103]
[98]
[104]
Liquid at
Liquid at
Liquid at
Liquid at
5.55
49.34
21
RTb
RTb
RTb
RTb
1.342
35.9
1.30
1.23
1.19
58.94
51.29
49.58
Tm/f: melting point/freezing point range, ChCl: choline chloride, U: urea, TU: thiourea, DU: dimethyl urea, EG: ethylene glycol, G: glycerol, TFA: 2,2,2-triuoroacetamide, TEG:
triethylene glycol, MPB: methyltriphenylphosphonium bromide, AA: acrylic acid, ZC: zinc chloride.
a
According to MSDS.
b
Not reported but liquid at room temperature (RT).
Table 2
Conductivity of some DESs, ILs and organic solvents.
Solvent system
Conductivity (mS cm1)
ChCl:Urea (1:2 M ratio)

ChCl:Ethylene glycol (1:2)
ChCl:Glycerol (1:2)
ChCl:Malonic acid (1:1)
ChCl:CrCl36H2O (1:3)
ChCl:ZnCl2 (1:2)
ZnCl2:Urea (1:3.5)
Ethylammonium chloride:Acetamide (1:1.5)
EMC:Ethylene glycol (1:3)
EMC:Glycerol (1:3)
MPB:Ethylene glycol (1:3)
MPB:Glycerol (1:3)
[EMIM][N(Tf)2]
[BMIM][N(Tf)2]
[EMIM][BF4]
[EMIM][PF6]
[BMIM][PF6]
Acetone
Ethanol
0.75 (25 C)
7.61 (25 C)
1.05 (25 C)
0.55 (25 C)
0.55 (30 C)
0.06 (42 C)
0.18 (42 C)
0.688 (40 C)
5.429 (25 C)
0.602 (25 C)
1.092 (25 C)
0.062 (25 C)
8.4 (25 C)
3.9 (25 C)
13.0 (25 C)
5.2 (25 C)
1.5 (25 C)
0.02 (20 C)*
1.345 106 (25 C)*
EMC: N,N-diethyl ethanol ammonium chloride, MPB: methyl triphenyl phosphonium bromide, [EMIM]: 1-ethyl-3-methylimidazolium, [BMIM]: 1-butyl-3methylimidazolium, [N(Tf)2]: bis(triuoromethylsulfonyl)imide, BF4: tetrauoroborate, PF6: hexauorophosphate.
The data are taken from references [7,17,24,26,27,105].
*
According to MSDS.
explore the mechanisms of electron-transfer reaction [19]. DESs

are characterized by high conductivities, viscosities, and surface
tensions, they also have lower vapor pressure in comparison to
other solvents [20]. Due to such benecial properties, they have
found plenty of various applications. In Table 1 a list of most common properties of DESs are presented.
1.3.1. Conductivity
Each material has a certain level capability to transmit electric
current which determine its electrical conductivity value. Various
factors play roles in this respect such as charge carriers available
in the material or as-called iconicity, their mobility and the temperature. For ILs case, less ionic conductivity range was found compared to aqueous electrolytes of high concentrated solutions.
Reduced ion mobility accounts for the moderate conductivities
caused by the presence of large-sized ions or ion aggregation
which affects the available charge carrier amount [21]. However,
ionic conductivity of ILs and DESs are dominated by their viscosity
Table 3
Comparison between the solubility (in ppm) of some MOs in three ChCl based DESs
and in two aqueous solutions of sodium chloride and hydrochloric acid at 50 C after
two days [18].
a
b
c
MO
DES 1a
DES 2b
DES 3c
NaCl
HCl
TiO2
V2O3
V2O5
Cr2O3
CrO3
MnO
Mn2O3
MnO2
FeO
Fe2O3
Fe3O4
CoO
Co3O4
NiO
Cu2O
CuO
ZnO
4
365
5809
4
6415
6816
5380
114
5010
376
2314
3626
5992
151
18,337
14,008
16,217
0.5
148
4593
3
10,840
0
0
0.6
0.3
0
6.7
13.6
30
5
219
4.8
1894
0.8
142
131
2
7
12
7.5
0.6
2
0.7
15
16
18.6
9.0
394
4.6
469
0.8
3616
479
13
12,069
0
0
0
2.8
11.7
4.5
22
4.0
3.3
0.1
0.1
5.9
36
4686
10,995
17
2658
28,124
25,962
4445
27,053
10,523
22,403
166,260
142,865
6109
53,942
52,047
63,896
DES 1:ChCl:Malonic acid (1:1 M ratio).

DES 2:ChCl:Urea (1:2 M ratio).
DES 3:ChCl:Ethylene glycol (1:2 M ratio).
Table 4
Solubility of sodium chloride in different DESs at 60 C [32].
DES
Molar ratio
Solubility w/100w
ChCl:Zinc(II) chloride
ChCl:Tin(II) chloride
ChCl:Tin(II) chloride:Zinc(II) chloride
1:1
1:2
1:3
1:3
1:1:1
43.68
60.00
63.00
2.08
4.27
in the rst place, therefore, temperature is also as important to

determine their conductivity [2224].
Giving a general description of DES conductivity as low or high
might me sometimes misleading. Researchers have usually mentioned the poor conduction of DESs when a comparison is made
with normal ILs [3,17,19]. This is because the higher viscosities
of some DESs compared to ILs [25]. By contrast DESs have been
widely considered as good conductors when compared with conventional organic solvents.
554
Examples for electrical conductivities of some common DESs,

ILs and organic solvents were collected and presented in Table 2
[7,2629]. Figures were found comparable sometimes to ILs and
gave the impression about the high chances of using DESs in electrochemical applications [30,31].
7%
1.3.2. Solvation properties

For all chemical and electrochemical synthesis technology it is
quite important to have a solvent or an electrolyte which is capable
of dissolving precursors during the reaction time and under synthesis conditions. Therefore, it is worthy to study the solvation
properties of solvents before we can determine where they can
be highly exploited.
Abbott et al. investigated the solubilities of Fe3O4, ZnO, CuO in
different DESs [6]. Various MOs and salts were then tested for their
solubility in DESs. Results were compared with the solubilities in
aqueous solutions of 0.181 mmol L1 NaCl and 3.14 mmol L1
HCl. All are summarized in the Table 3 below.
In different types of DESs, various solubility values were
reported for some types of sodium salts at different temperatures
and for a range of mole ratios (salt:HBD). In general, most of the
results showed that increasing the temperature and decreasing
the molar ratio can increase the solubility. It was also found that
the chemical structure of the DES affects the sodium salts solubility
[32]. High sodium salts solubility in certain types of DESs can be
employed very well in electrochemistry if they are used as electrolytes to produce sodium metal at mild temperatures. Some
examples are given in Table 4 to illustrate the different solubilities
of NaCl salt in some types of DESs. Molar ratio effect was also
investigated for one of the studied DES.
93%
ILs & Nanotechnology

DESs & Nanotechnology
Fig. 2. The proportion of DES and IL articles in nanotechnology elds.
contribution in nanotechnology was placed for carbon nanomaterial projects. Silica nanoparticles come in the second place
in terms of their applications with ILs.
IL applications have been spread over a wide range of elds
such as chemical and biochemical reactions, electrochemistry,
polymer science and nano-chemistry [34]. However, tendencies
of DES use are same for those of ILs. So far, all recently reported
DES applications in nanotechnology have already been studied
before for IL before but with the use of ILs instead. This means
there is still a wide range of possibilities to employ DESs as alternatives to ILs in nano-science as the last (ILs) have paved the road
for that since 2001. In this review, we aim to summarize the recent
roles of DESs played in every eld of nanotechnology. A list of DESs
that have been used so far in nanotechnology eld is provided in
Table 5 .
In fact, ILs have shown a special properties when they are in
nano-quantities, either if they are conned in nano pores of nanostructured materials [35,36] or are interdependently existed in
nano-scale volumes like nano-droplets [37] and nano-lms [38].
Most nanomaterials are likely to aggregate with each other
naturally [39,40]. This may limit their benign properties required
for particular applications like the capability to absorb certain
compounds. Another negative aspect for aggregation is the complication for any modifying process to attain better exploitation
in some applications such as sensors and biosensors. To tackle
these difculties, ILs have emerged as green alternatives to volatile organic solvents [41]. They have been considered as convenient
media to disperse, solve, and split nanomaterials. Particularly, due
to the ability of ILs and DESs as their analogs to interact with some
2. Main applications of DESs in nanotechnology

The rst combination of nanotechnology and ILs was published
in 2001 [33], however, the one related to DES was reported as late
as 2008 introducing the use of the DES a solvent for the chemical
synthesizing of gold nanoparticles. Later on, several examples in
nanotechnology elds were reported on the use of DESs, see Fig. 1.
Among the whole articles that have been published since 2001
combining ILs or DESs with nano-science, there are 45 articles
studying DESs, over about 673 articles on ILs. This includes almost
40 review articles covering some areas of IL applications in nanotechnology, see Fig. 2. In addition, there are more than 500
patents studying various types of using ILs/DESs in nano-led
science.
Carbon nanomaterials (CNMs) such as graphene, single-walled
and multi-walled carbon nanotubes (SWCNTs and MWCNTs
respectively) have received a considerable concern in this respect.
According to our statistics, approximately 50% of the IL
800
673
Number of Arcles
700
564
600
500
392
400
301
300
200
55
92
154
223
45
34
29
24
18
100 1
13
11
6
5
3
3
1
0
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014
ILs & Nanotechnology Arcles
Year
DESs & Nanotechnology Arcles

Fig. 1. Trends of article number studying the application of DESs and ILs in nanotechnology.
555

Table 5
DESs used so far in nanotechnology and their main roles.
DES
Molar ratio
Role
Ref.
ChCl:U
1:2
ChCl:1,3DU
ChCl:TU
ChCl:EG
2:1
1:2
1:2
1:2
ChCl:CrCl3.6H2O
ChCl:AA
ChCl:PTSA
ChCl:HMP
ChCl:ZnCl2
ChCl:GA:G
ChCl:MA
CA:DU
1:2
2.3:12.0:11.6:11.3:1
1:1
1:1
1:1
1:0.25:0.25
1:1
1:1.5
Electrolyte (nanostructure sensor)

Media for nanoparticles production by sputter deposition technique
Electrolyte (nanoparticle deposition)
Media for chemical synthesis of nanoparticles
Dispersant
Exfoliation
Dispersant
Nanodroplet embedded in microstructure
Dispersant and media for chemical synthesis of nanoparticles
Structure-directing agent and media for chemical synthesis of nanoparticles
Dispersant
Nano-connement
Structure-directing agent and media for chemical synthesis of nanoparticles
Nanocatalytic assembly
[63]
[67,68]
[77,8084,106110]
[6973,75,94,111117]
[77]
[57]
[118]
[86]
[52]
[76,78,79,107,110,119123]
[74,124126]
[93]
[127]
[85]
[58]
[128]
[91]
[129]
[49]
[64]
ChCl: choline chloride, U: urea, DU: dimethyl urea, TU: thiourea, EG: ethylene glycol, AA: acrylic acid, PTSA: para-toluene sulfonic acid, HMP: tris(hydroxymethyl) propane,
GA: gallic acid, G: glycerol, MA: malonic acid, CA: citric acid.
nanoparticles, many cases have been reported regarding the dispersion of solid nanomaterials.
In synthesis chemistry, it is generally believed that solvents are
of essential signicance in all synthetic processes [42]. It is worth
mentioning that the main role of these solvents is to homogenize
all the reagents in the reaction media. Organic and non-organic solvents have been widely used, they are chose depending on the
reaction peculiarities and how the solvent may deal with them.
The same criterion is followed in nanoparticle synthesis.
Recently, ILs and DESs have been the solvent of choice for the convenient synthesis of nanoparticles due to thermal stability, good
dispersibility, large ionic conductivity, wide electrochemical window [43]. Two different routes of nano-synthesis can be carried
out by using ILs/DESs as solvents for chemical syntheses or electrolytes for electrochemical ways.
In a recent study [44], DESs were reviewed for their recent
applications as designer solvents to produce different sorts of
nanomaterials. Nanomaterial productions were dened in this
study in 6 aspects: shape-controlled nanoparticles, electrodeposited lms, metalorganic frameworks, colloidal assemblies,
hierarchically porous carbons, and DNA/RNA architectures. The
role played by DESs was investigated deeply on how to direct
chemistry at the nanoscale. According to literature, DES can act
as template, carbon or metal source and as a reactant or auxiliary
agent in nanomaterial production. The reactivity of DESs was found
affected by many factors such as hydrogen bonding, surface tension, viscosity and polarity.
There has to be known that there are a plenty of elds for the
use of original ILs in nanotechnology, but those for their analogs
(DESs) are still few in comparison. Our goal here is to cover the
recent occupation of DESs in every single area of nanotechnology.
This work is organized to give a complete and concise summary
looking at subjects from a broader perspective. Hopefully, this will
add an engineering-looking character to the work away from
chemistry sophistication.
2.1. Media to disperse nanoparticles and control morphology

Agglomeration tendency of nanoparticles is one of the basic
challenges limiting their applications. It leads to a considerable
decrease in the surface, and as known, the lower surface area, with
respect to the bulk volume, the lower chemical and catalytic activity of the particles.
Generally, metal nanoparticles can only show good stability in
their suspensions by the coordination of some kinds of surfactants.
These surfactants somehow help prevent nanoparticles agglomeration by forming a protective layer surrounding the surface [45].
Uniquely, ILs as liquid solvents with a special ionic nature have
the ability to act as satisfying stabilizers for a wide range of nanoparticles even without using any surfactants [41,46]. The importance of such dispersion media is hugely considered, either early
during the nanomaterial synthesis or later for preparation of further application. The last is to obtain special properties and/or
get as higher benet as possible.
For rst stages of nanomaterial production, it is highly signicant to choose a suitable solvent which can effectively prevent
products from being bundled or cluster-assembled. ILs and DESs
have been widely used as efcient dispersants during the synthesis
reaction of nanoproducts. They have played roles in determining
the shape, size and morphologies [4749]. They are also capable
of splitting small-scale structures into nano-scale and this aspect
is added to their use as a functional dispersing solvent. Many
examples of graphene-ILs hybrids fabrication, obtained by using
ILs solvents for carbon nanotube (CNT) or graphite exfoliation, support this case [50,51]. After nanomaterials production, ILs may be
used to form nano-hybrids (i.e. nanouids or nanocomposites) in
order to enhance special properties of the nanomaterials in the
mixture or get the mixture itself ready for certain application.
However, in spite of the large number of articles discussing the dispersibility of nanomaterials in ILs, the reported cases of using DESs
for the same purposes are still few in comparison, but they are
existed at least. The aim of the following sections is to cover and
summarize all relevant cases available so far for different DES dispersing purposes.
2.1.1. Dispersants for nanomaterials to form nanocomposites and
nanouids
As mentioned earlier, the contribution of DESs in nanomaterial
dispersion is still limited. Up to date, there is no large number of
deep studies reporting the dispersibility of nanomaterials in DESs
as there is for ILs. Table 6 is summarizing some of the related cases
of DES as dispersants. Examples were selected from studies where
readers can nd at least a mentioning about the DES ability to
556
Table 6
Examples of the use of DESs as efcient dispersants.
DES type
Type of dispersed
nanomaterial
Dispersion purpose
Remarks & details
Ref.
DES is polymerizable solvent helped to disperse

substances and incorporate carbon nanotubes
The composite has great potential in
biomedicine, energy and environmental
applications
DES helped in high dispersed-phase loadings of
electrodeposited Ag
Improved lm properties compared to pure
metal
Longer storage time was noted for epoxy
composition containing DES (more than 60 days)
DES could act as an effective GNP dispersing
medium, which positively affected electrical
volume resistivity of epoxy composites
Poor dispersion stability in DES was reported for
P-MWCNTs while it was very high for OMWCNTs (1 year)
[85]
Type of salt
(component
1)
Type of HBD (component 2)
Molar
ratio
(Salt:HBD)
ChCl
Acrylic acid
2.3:1
2.0:1
1.6:1
1.3:1
MWCNT
Synthesis of
macroporous
poly(acrylic acid)CNT
composites
ChCl
Ethylene glycol
1:2
SiC and Al2O3

nanoparticles
ChCl
Tris(hydroxymethyl)propane
1:1
Graphite
nanoplatelets
(GNP)
ChCl
Urea
1:2
Pristine MWCNTs
(P-MWCNTs) and
oxidized MWCNTs
(O-MWCNTs)
Electrodeposition of Ag
and formation of Ag/
SiC/Al2O3
nanocomposite lm
DES as epoxy resin
curing agent to
fabricate GNP/DES/
epoxy resin
nanocomposite
Electrodeposition of Ni/
MWCNT composites on
copper substrate
(coating)
Fig. 3. Pictorial imagination for the dual functionalized DNA hybrid material [52].
disperse nanoparticles during their preparation even it is for

another intended application.
To give a clear example, a study was conducted recently regarding the ability of DES for DNA solubilization. In this study, Mondal
et al. [52] investigated the suitability of using DES for dual functionalization of DNA (Salmon testes). The process was carried out
using Fe3O4 nanoparticles and protonated layered dititanate sheets
(H2Ti2O5H2O) as functionalizing agents in DES medium of
ChCl:ethylene glycol (1:2 M ratio). Eventually and after 6 h, hybrid
material was obtained with antibacterial and magnetic properties
see Fig. 3. High pure DES was successfully recycled and reused
for solubilization following the same method. The study involved
also DNA stability in the hybrid material and applications were
suggested in biosensing and biomedicine elds.
2.1.2. Media to split nanomaterials
The hallmark of nanomaterials is to have in the number size distribution at least 50% of particles with one or more external dimensions in nano size (i.e. between 1 and 100 nm) [53].
Some micro-structures are in fact a group of bundled particles
in nano-size but they are stuck together in somehow to form larger
structures. Graphite for example, is a multi-layer graphene sheets
with a much larger overall external dimension [54,55]. If the graphene sheets are rolled to form cylindrical shape, CNTs will be
formed. Hence, rolling one graphene sheet layer leads to SWCNTs
but to have seamless cylinders of more layers, multi graphene layers need to be rolled and MWCNT is formed [56]. Based on deep
[119]
[128]
[77]
understanding of those facts, many researches have been conducted to nd out how we could unbundle the bulky aggregation
of materials to reach their smallest possible formula. Later, this
process was called exfoliation or split of nanomaterials.
DESs are holding some similar properties with IL and thus play
the same role that could be played by ILs in some area of applications. However, it seems that the door of applying DESs to split or
exfoliate small-sized materials has just been opened. A recent
study done by Boulos and co-workers [57] revealed the transformation of human hair into functional nano-dimensional material using ChCl:Urea DES (2:1 M ratio, respectively). SEM results
showed that before DES treatment a typical hair was observed with
around 50 lm diameter and some cuticle cells about 5 lm size
were covering the hair surface. After hair treatment with DES, it
was clearly seen that cuticle cells were completely exfoliated from
hair. More analyses were conducted to recognize the size and morphology of the exfoliated cuticle cells. TEM images detected small
particles in large numbers with a granular morphology which are
probably melanin pigments of hair cells. These small particles were
also in nano-size (1520 nm) as HRTEM images showed. What is
more, TEM images proved the presence of macrobrils nano-rods
with a diameter of around 200 nm which may be existed due to
unraveling of cortical cells to their nano-structural components
under the DES effect especially in protein denaturing.
2.1.3. Media to obtain special sizes and morphologies of nanomaterials
The role of ILs and DESs as morphology directing agents for the
produced materials was frequently investigated in various studies
when they are included in the reaction media. In fact, apart from
the role as reaction media which will be discussed later in details,
IL and DES natures were found to play a crucial role in determining
the size and morphology of the produced nanomaterials. Changes
might take place either during the production reaction or after
reaction for dispersing purposes in colloidal applications. In this
section, we aim to report some cases where the effect of DESs on
shape, size and morphology is investigated. Sometimes it is
referred to template to describe this role of DES.
Gutirrez et al. [58] reported the functions of DES based on ChCl
and para-toluene sulfonic acid (1:1 M ratio) in a process to prepare
a porous carbon. The DES was used as a media and catalyst for furfuryl alcohol condensation. In addition to that, it was a media for
the following carbonization process to produce different porous
carbon monoliths including MWCNTs. Researchers found that the

used DES acted also as structure-directing agent for the produced
carbons. DES segregations were found to be responsible for forming macroporous network during polycondensation.
Oh et al. [49] used a DES of ChCl and malonic acid as both a
reaction medium and structure-directing agent to synthesize
highly monodisperse gold microparticles. The product had a distinctive surface nanoroughness and highly dened diameters controlled precisely under different reductive conditions. The
synthesis was not supported by any surfactants or polymers, suggesting that the DES has essential role as a structure directing
reagent and particle stabilizer. Different structures were obtained
at different temperatures (At 70 C, isotropic small particles with
almost 100 nm diameter, whilst three-dimensionally networked
nanostructures were obtained at 90 C). This was explained by
the highly dependency of the DES properties on temperature.
2.1.4. Electrolytes for electrochemical systems with nanostructured
electrodes
Many studies have covered the use of ILs as electrolytes in electrochemical systems such as sensors, actuators, capacitors, batteries, solar and fuel cells [5962]. All these systems need of course
highly specied requirements from every involved component to
be serving properly. In fact, the use of ILs as elements in electrochemical devices has been well identied. ILs electrolytes are
becoming very popular in electrochemistry applications in general
and when nanomaterials are accompanied in particular. However,
only a single study was reported so far for DES use in electrochemical sensing. In 2014, Zheng et al. [63] used a mixture of PH 4.0 acetate buffer solution with a ChCl:Urea DES (1:2 M ration respectively)
as an electrolyte for the electrochemical sensing of quercetin.
MWCNTs modied graphite electrode was used as a working electrode in a three-electrode system with platinum and saturated
calomel as auxiliary and reference electrodes respectively. They
obtained a good linear relationship between quercetin concentration in the electrolyte and the oxidation peak current within concentration range from 9.95 107 to 4.76 107 mol L1. This
method was found much easier and less expensive than the IL/
CNTs composite modied electrodes system used for the same
purpose.
2.1.5. Media to produce efcient and recyclable nano-catalytic
assembly
For the synthesis of Imidazo[1,2-a]pyridines, Lu and coworkers
[64] have developed a recyclable efcient nano-catalytic system to
be used for the reaction. The optimum catalytic system achieved
was based on CuFeO2 nanoparticles in a eutectic solvent of citric
acid-dimethyl urea melt (1:1.5 M ratio). The study involved a series of reactions using three-based components as reactants,
namely 2-aminopyridine, aldehydes and alkynes. Reactions were
rst run using various solvents as a part of the catalytic system
such as toluene, ethanol, dimethyl formamide as well as some
types of DESs. Copper salts along with different metallic oxides
nanoparticles were subjected to testify their catalytic efciency.
Eventually, the system of citric aciddimethylureaCuFeO2 nanoparticles was selected based on the best resulted yield, 95%. This
catalytic assembly was then used for the further optimization of
reaction time and temperature. However, according to this study,
DES has helped not only to recover the catalyst nanoparticles (kept
same efciency for 6 times) but also it played a catalytic role
because of its acidity.
2.2. Reaction media for nanomaterial production
When using ILs as solvents, nanomaterial production can be
achieved in many different ways: (1) chemically, (2)
557
electrochemically, (3) photochemically, (4) sonochemically (using

ultrasound technique), (5) by microwave irradiation, (6) by gasphase synthesis using sputtering, (7) or by plasma electrolysis
[45]. This section illustrates the recent applications of DESs as solvents or liquid media in nano-synthetic chemistry and
electrochemistry.
2.2.1. Solvents and reactants for the physicochemical synthesis of
nanomaterials
ILs were accompanied with the eld of reaction chemistry
through the use of chloroaluminate(III) ILs. During 1990s, neutral
ILs were developed and a wide range of reactions were performed
and spread rapidly [65].
DESs are classied as a type of green solvent with many prominent advantages for chemical synthesis of nanomaterials in many
references. DESs were not only used as solvents, in some cases they
were also used as reactants to produce the intended nanoparticles.
In this respect they played multiple roles as a solvent and precursor at the same time. All aspects of DESs in chemical synthesis of
nanomaterials are summarized in Table 7 as shown below. Each
one is described through: type of DES, type of nanomaterial produced, reaction method, composition and conditions. In this table,
it is clear that ChCl:Urea based DES have been used mostly for
chemical syntheses of nanomaterials especially metal oxide
nanoparticles.
2.2.2. Electrolytes for nanomaterial electrodeposition
Electrodeposition is a process leading to the formation of solid
materials by electrochemical reactions in a liquid phase.
Passivation phenomenon is one of the basic problems inhibiting
the deposition progress as a result of poor electrolytic solvation
ability toward metal oxides and hydroxides. As mentioned earlier,
high solubility of metal oxides, salts and hydroxides in DESs gives
them bonus prominence over conventional electrolytes based on
aqueous solutions or organic solvents [26].
The most popular electrodeposition setup is composed of a
three-electrode electrochemical cell (a specially designed cathode,
a counter electrode or anode and a reference electrode [66]). A
direct current method with a two-electrode system can also be
used for nanoparticle electrodeposition. Simply in this process,
positive metallic ions of the electrolyte are reduced at cathode
electrode and form neutral metal particles deposited on the surface. Applications of metal electrodeposition technique include
photoactive semiconductors, corrosion-resistant functionalized
surfaces, developing the magnetic properties of materials and
building up functional components for electronic industries such
as circuit boards.
DESs have been widely used as electrolytes to produce nanoparticles electrochemically. With a setup of two or three electrodes,
DESs have been successfully used as electrolytes and in similar techniques used for ILs beforehand. All available examples for this case
are described in Table 8. ChCl:Urea based DES have taken the rst
place in this respect regarding the number of studies it is involved
in. This DES was the most common electrolyte especially for platinum and palladium electrodeposition. While, ChCl:ethylene glycol
based DES have come in the second place with most interests shown
for Ni nanostructures compounds electrodeposition.
2.2.3. Media for sputter deposition to produce nanoparticles
There are several effective synthesis methods for nanoparticles
such as chemical synthesis, microwave assisted synthesis and
physical vapor deposition (PVD). In fact, physical sputtering
deposition has been shown to offer a clean strategy for forming
NPs on solvent surface with low vapor pressure such as ILs and
DESs.
DES type
558
Table 7
Chemical and physicochemical nanomaterials production by the means of DESs as reaction media.
Reaction medium and composition
Reaction type
Remarks/conditions
Ref.
Macroporous poly(acrylic acid)CNT

composites
DES with ethylene glycol

dimethacrylate (EGDMA) as crosslinker
and benzoyl peroxide as a thermal
initiator
100 ml 0.05 M of SnCl2.2H2O in
DES + 4 ml of H4N2.H2O 85% (slowly)
FeCl3.6H2O and K4Fe(CN)6.3H2O were
added separately into DES
Frontal
polymerization
process
At 130 C
[85]
Homogeneous
precipitation
Coordination of
Fe(CN)-4
6 ion with
Fe3+ ion in the
DES
Co-precipitation
At room temperature (25 3 C)
[124]
At 80 C
[118]
1st Step: 600 rpm and 80 C for 20 min

2nd Step: 600 rpm and 80 C for 1.5 h
[111]
Combining the
Pb2+ and S2precursors in hot
DES
1st Step: stirring at 80 C

2nd step: stirring both of solutions in an oil bath
at 80 C until transparent
3rd Step: using a ask with a condenser to
mixing at 140 C till the solution turns black
[115]
Ionothermal
strategy
For Ni(NH3)Cl2 and nanosheet-like NiCl: Teon

autoclave 150 C for 4 h
For Ni(NH3)Cl2 and nanosheet-like NiCl: heated
under ambient atmospheric pressure
[94]
Ionothermal
strategy
At 323 K in N2 for 30 min

then 423 K, during which the solution turned
black from light green with violently release of
gases (as bubbles) for 5 h
The suspension (DES + CNT) was stirred for 24 h
at room temperature before addition of FA
polycondensation and carbonization: FA +
(DES + CNT) suspension, the resulting solution
was vortexed for 2 min and treated thermally
(rst at 37 C for 8 h and then at 90 C for 4 days)
The resulted condensed FA polymers treated for
4 h at 210 C followed by another 4 h at 800 C
(1.0 C min1 heating ramp) under a N2
atmosphere
Reaction time is 1 h, reaction temperature is
25 C in the presence of polyvinylpyrrolidone
(PVP) in DES
[69]
2nd Step: ultrasonically (200 W) for about 4 h
[125]
Salt
HBD
Molar ratio
(Salt:HBD)
ChCl
Acrylic acid
ChCl
Ethylene glycol
2.3:1
2.0:1
1.6:1
1.3:1
1:2
ChCl
1,3-Dimethyl
urea
ChCl
Urea
1:2
Spherical Fe3O4 magnetic

nanoparticles
ChCl
Urea
1:2
PbS nano/micro superstructures
ChCl
Urea
1:2
ChCl
Urea
1:2
ChCl
para-Toluene
sulfonic acid
1:1
Nanostructured Ni compounds:
nanocrystals Ni(NH3)6Cl2nanosheetlike NiCl2nanoower-like aNi(OH)2mesoporous, nanoower-like
NiO
Nickel phosphide nano-particles
Ni2P (25%) supported on amorphous
and mesoporous
Ni3(PO4)2-Ni2P2O7
Hierarchical porous MWCNT
composites
ChCl
Urea
1:2
CuCl nanoparticles
ChCl
Ethylene glycol
1:2
SnO2/reduced graphene oxide

nanocomposite
SnO2 nanocrystalline
Prussian blue nanospheres
1st Step: 2.164 g (8 mmol) of FeCl3.6H2O

and 1.194 g (6 mmol) of ground
FeCl2.4H2O were added to 15.585 g of
DES
2nd Step: adding 2.613 g (46.7 mmol) of
KOH to the mixture
1st Step: solvent Preparation
(6 mL) deionized water + 30 ml DES
2nd Step: Preparation of solutions:
Sol 1: (12 mmol, 0.9134 g)
thioacetamide + 12 ml from solvent
Sol 2: (12 mmol, 5.3206 g) lead(IV)
acetate + 12 ml solvent
3rd Step: mixing Sol 1 + Sol 2
DES + NiCl2.6H2O
For Ni(NH3)Cl2 and nanosheet-like NiCl:
0.5 M NiCl2 in DES
For nanoower-like a-Ni(OH)2 and
nanoower-like NiO: 0.1 M NiCl2 in DES
27.92 g (0.2 mol) of ChCl + 24.02 g
(0.4 mol) of urea + 5.94 g (0.02 mol) of
Ni(H2PO)2.6H2O + 1.66 g (0.02 mol) of
NH4H2PO2
functionalized MWCNTs (0.01, 0.03 and
0.05 g respectively) + (1.0 g) DES +
(0.20 g) furfuryl alcohol (FA)
(14 mL) DES containing

polyvinylpyrrolidone PVP + (2.2232 g)
CuCl2.2H2O + (1.3754 g) ascorbic acid +
(50 mL) hydrochloric acid (0.1 mol.L1)
1st Step: solutions preparation
Sol 1: 40 mg GO + 100 ml DES
Sol 2: 2.25 g SnCl2.2H2O + 100 ml DES
2nd Step: mixing sol 1 + sol 2
furfuryl alcohol
(FA)
condensation
catalyzed by a
protic DES
Oxidation
reduction
reaction
Oxidation
reduction
reaction between
Sn2+ and
graphene oxide
[58]
[112]
Nanomaterial produced
Table 7 (continued)
DES type
Reaction type
Remarks/conditions
Ref.
1:2
a-chitin nanobers
Solvation
Stirring at 500 rpm at 100 C for 2 h
[86]
Ethylene glycol
1:2
Nanoporous Ag lm
DES with 10%, w/w Pure chitin powder

then adding 10 mL of distilled water
0.01 or 0.1 M AgCl in DES
Urea
1:2
Gold Nanoparticles
25 mL DES + L-ascorbic acid (0.05 g) +

HAuCl44H2O (0.015 g)
At room temperature 22 (2 C) or at 50 C, by
immersing a cleaned copper alloy foils into AgClDES solution without stirring
At 30 C, under magnetic agitating
[126]
ChCl
ChCl
Urea
1:2
nano-sized SnO crystals
Galvanic
replacement
reaction
Reduction of
HAuCl4 by Lascorbic acid
Ionothermal
strategy
Facile, green
antisolvent
approach
Salt
HBD
Molar ratio
(Salt:HBD)
ChCl
Thiourea
ChCl
At 100 C with a heating rate of 5 C.min1 under

vigorous stirring
At 70 C water bath, vigorous stirring for 30 min
[116]
Reduction of
HAuCl4 by DES
Continuous stirring under ambient conditions
[129]
Homogeneous
precipitation
50 mL 0.1 M NiCl2/DES in a three-neck ask

under ambient atmosphere pressure at 150 C for
40 min.
Followed by adding 10 mL deionized water under
vigorous magnetic stirring.
After another 20 min reaction, cooling in ice bath
Stirring for 3 h at 50 C
[117]
Urea
1:2
Cu -doped ZnO nanocrystals
ChCl
Gallic acid:
glycerol
1:0.25:0.25
gum Arabic coated gold nanoparticles
ChCl
Urea
1:2
Mesoporous NiO
ChCl
Malonic acid
1:1
Gold Microstructures with Surface

Nanoroughness
200lL (0.15 M) HAuCl4 + 20 mL of

DES + 200lL of (0.1 M) ascorbic acid
ChCl
Urea
1:2
Fe2O3 nanospindles
0.1 M FeCl36H2O in DES
ChCl
Urea
1:2
Ni layered double hydroxide (Ni LDH)

as a-Ni(OH)2 nanoowerNi
nanoparticlesNi mesoporous owerlike structure
0.1 M NiCl2 in DES
Ionothermal
strategy
ChCl
Urea
1:2
Co Fe layered double hydroxide (CoFe

LDH) nanosheets
0.1 M Co+2 and 0.035 M Fe+3 in DES from

CoCl26H2O and FeCl36H2O
Ionothermal
strategy
ChCl
Urea
1:2
Mesoporous Co3O4 sheets or

nanoparticles
0.1 M CoCl2 in DES
Ionothermal
strategy
Reduction of
HAuCl4 by
ascorbic acid
Ionothermal
strategy
40 mL of 0.1 M FeCl36H2O/DES in a three neck

ask, at 200 C, under ambient atmospheric
pressure
Followed by adding 40 mL deionized water with
vigorous stirring for 10 min
Then cooling rapidly with ice
1st step: 50 mL of 0.1 M NiCl2/DES in a three neck
ask, at 150 5 C, under magnetic stirring
2nd step: annealing the resulted Ni LDH under Ar
atmosphere at 300 C for 4 h with and without
OCN- addition
50 mL of Co+2,Fe+3/DES in a round-bottom ask,
at 210 5 C, under magnetic stirring
Followed by adding deionized water
50 mL of 0.1 M CoCl2/DES in a three neck ask, at
150, 180, and 210 C, for 40 min under magnetic
stirring
Followed by adding 100 mL deionized water with
vigorous stirring for 1 min
[114]
[49]
[75]
[71]
ChCl
2.25 g SnCl2.2H2O was dispersed in

100 ml DES
1st step: 0.36 g of ZnO powder + 150 g of
DES
2nd step: bad solvent preparationequal
volumes of deionized water and
ethylene glycol
3rd step: 5 mL of ZnO-containing DES
was injected into 160 mL of the bad
solvent
Aqueous solution of DES 0.01% (w/v) +
15 mg gum Arabic + (0.05 M) HAuCl4 in
different volumes
0.1 M NiCl2 in DES
2+
[113]
[72]
[73]
(continued on next page)

559
1st step: 50 ml of 0.5 M MnCl2/DES in autoclave

at 120, 150, and 180 C, for 4 h
Cooling down to room temperature then washing
the MnCO3 precipitates with methanol and water
and ethanol, centrifuging and drying
2nd step: annealing the MnCO3 at 300 C for 4 h
then gradual cooling process to room temperature
50 ml of reaction solution in DES in a three neck
ask, at 150 C, for 3 h
Cooling down to room temperature then
centrifuging the precipitate accompanied by
washing with deionized water and methanol, and
drying under vacuum
Ref.
Ionothermal
strategy
A mixture of NiCl26H2O and
NaH2PO2H2O in DES, molar ratios
(1:0.2)
Ethylene glycol
ChCl
1:2
NiP alloy nanoparticles
Ionothermal
strategy and
facile thermal
conversion
process
Urea
ChCl
1:2
MnCO3 mesocrystals nanowire-like

MnOx
0.5 M Mn+2 in DES from MnCl2.4H2O
Remarks/conditions
Reaction type
Molar ratio
(Salt:HBD)
HBD
Salt
DES type
Table 7 (continued)
[74]
[70]
560
Raghuwanshi et al. [67] reported the formation and growth

mechanisms of gold nanoparticles (AuNPs) in eco-friendly deep
eutectic solvents (DES; ChCl and urea). Gold nanoparticles were
formed in DES by using a low-energy, soft-sputtering deposition
technique under very clean conditions in a vacuum chamber.
This low-energy deposition technique allowed synthesizing
AuNPs either directly or in a sequential way with diameters over
a wide range from 1 to 100 nm.
Data analysis revealed that for a prolonged gold-sputtering time
there was no change in the size of the particles. Only the concentration of AuNPs increased linearly in time. More surprisingly,
the self-assembly of AuNPs into a rst and second shell ordered
system was observed directly by in situ SAXS for prolonged goldsputtering times. The self-assembly mechanism was explained by
the templating nature of DES combined with the equilibrium
between specic physical interaction forces between the AuNPs.
Later on, the same group [68] aimed in other work to estimate the
effect of sputtering time on the structure parameters and to evaluate
the growth mechanisms of the AuNPs. They managed to establish a
deep understanding of the time dependent growth and the stability
of AuNPs with respect to the effect of ionic liquids as surrounding
environments. The results showed formation of spherical nanoparticles with a mean diameter of 50.5 nm, see Fig. 4. For extended
sputtering times, the number density of AuNPs increased linearly
and a very pronounced 1st and 2nd shell ordering was observed.
For shorter gold-sputtering times of 30 s the gold atoms started to
aggregate on the surface, however, prolongation of gold-sputtering
time led to an increase in the concentration of gold atoms on the
DES surface. After dispersion into the bulk they self-organized into
closed-packed ordered domains (clusters of AuNPs).
2.2.4. DES-based nano production: an overview about applications,
advantages and challenges
From previous examples, DESs have shown a versatility to be
used in different reaction methods. They provide a platform to
serve the several physicochemical reaction types perfectly such
as ionothermal reaction, precipitation, polymerization, condensation and reductionoxidation reactions including replacement reactions.
Nanostructured materials obtained ionothermally using DES
media were found highly valuable in various application. The benets of DESs exceeded being safe, cheap and convenient alternative
to conventional solvents. Their role to determine shape, size and
morphology seemed to be controllable which considered as important to reach the required efciency in advanced application.
Production of nanostructured catalysts for example is still a challenge requiring the efforts to adjust their synthesis conditions.
Zhao et al. [69] produced Ni2P nanoparticles supported on mesoporous and amorphous Ni3(PO4)2Ni2P2O7 using ChCl:Urea based
DES as media for ionothermal reaction. Produced nanostructured
system showed catalytic activity for hydrodesulfurization of dibenzothiophene, hydrodenitrogenation of quinoline and hydrogenation of tetralin. Ionothermal method in ChCl:Urea media can also
fabricate calcite type MnCO3 biominerals with mesocrystal structure [70]. The porous and nanowire-like MnOx nanostructures
can be obtained through a facile thermal conversion process from
the diverse MnCO3 precursors, which are demonstrated as effective
and efcient adsorbents to remove organic waste (e.g. Congo red)
from water.
Layered double hydroxides (LDHs) such as (a-Ni(OH)2, aCo(OH)2 and FeCo LDH) and the derived metal oxides can be
ionothermally synthesized from DES based reaction system.
These nanomaterials can be used as potential energy storage electrodes [7173].
Anode materials with nanostructures for application in lithium
ion batteries can be synthesized from DESs. Amorphous and
Table 8
DES-based electrolytes for nanoparticles electrodeposition.
DES type
Electrolyte composition
Electrochemical cell information

Anode (counter
electrode)
Cathode (working
electrode)
ChCl/urea/PdCl2
Nano-sized Pd
lm
Pd sheet
Rotating Cu
substrate
1:2
19.3 mM H2PtCl6 DESs

solution
Pt nanoowers
Pt wire
Glassy carbon disk

(GC, 3 mm)
Pt quasireference
electrode
Urea
1:2
19.3 mM H2PtCl6 DESs

solution
Triambic
icosahedral
(TIH) Pt
nanocrystals
(TIH Pt NCs)
Pt wire
Glassy carbon (GC)
Pt
Programmed
electrodeposition
routine three
electrode system
ChCl
ChCl
Urea
Ethylene glycol
1:2
1:2
Platinum 1 mm or
2 mm diameter,
made in-house
Ag wire
quasireference
electrode
Ethylene glycol
1:2
Nano-structured
Cu (bright
metallic
coatings)
Nanostructured
Ni lms
Pt
ChCl
0.1 M [CuCl2 2H2O] in

DES with 10 wt%
0.05 mm Al2O3 or 10 wt%
13 mm SiC
1 M NiCl26H2O in DES
Electrolytic Ni
plate
Brass (Cu0.64Zn0.36
alloy)
Potential step
chronoamperometry,
three-electrode
system
(a) constant voltage
mode (CVM), (b) pulse
voltage mode (PVM),
and (c) reverse pulse
voltage mode (RVM),
two-electrode system
ChCl
Ethylene glycol
1:2
Mixture of either Al2O3

(50 nm) or silicon carbide
(50 nm or 2 mm) with
DES
Iridium oxide
coated Ti mesh
Ni substrate
Constant potential
difference, twoelectrode system
ChCl
Ethylene glycol
1:2
DES containing 0.3 M

NiCl26H2O
Ag
nanocomposites
with nanoalumina
particles or SiC
nanoparticles
Nanostructured
NiO lms
Ni plate
Direct current (DC),

ChCl
Ethylene glycol
1:2
ChCl
Ethylene glycol
1:2
ChCl
Urea
1:2

NiCl26H2O, 0.1 M KMnO4
and 0.1 MH2O2
DES containing 1 M
NiCl26H2O
SmCl3 + 0.018 M CoCl2
indium tin oxide

(ITO) glass with
3 cm 2.5 cm
ITO glass of 3 2.5
cm2
ChCl
Urea
1:2
HBD
Molar
ratio
(Salt:HBD)
ChCl
Urea
1:2
ChCl
Urea
ChCl
19.3 mM H2PtCl6/DESs
Nanostructured
NiO lms
Ni plate
Nanocrystalline
Ni lm
Samarium and
cobalt SmCo
Nanostructures
Electrolytic Ni
plate
Pt spiral
Brass foil
(Cu0.64Zn0.36 alloy)
Vitreous carbon rods,
copper and nanoporous alumina
templates (50 nm
porous diameter)
Pt Nanocrystals
Pt wire
Glassy carbon disk

(GC, U = 3 mm)
Reference
electrode
Electrodeposition
method
Electrodeposition conditions & remarks
Ref.
Applying direct
current (DC) or pulse
current plating (PP),
Cyclic voltammetry
(CV), three-electrode
system
At 70 C, plating time 90 min, The

applied current density for DC plating
j = 0.05, 0.1 and 0.2 mA cm2 and for PP
plating jav = 0.1 mA cm2
At 80 C, potential scan range: 1.5 to
0.2 V, scan rate of 50 mV s1 and 80
cycles, electrodeposition occurs at 1.29
V
At 80 C, the electrochemical potential
was rstly stepped from open circuit
potential (OCP) to nucleation potential
(EN) of 1.80 V (vs. Pt), and then stayed
at EN for 45s to generate Pt nuclei on the
GC electrode surface. The development
of the Pt nuclei into TIH Pt NCs was
achieved by applying a square-wave
potential (f = 10 Hz) with the lower (EL)
and upper (EU) potentials of 1.30 and
0.30 V, respectively
At 20 2 C, at various scan rates: 10 to
50 mV s1 under diffusion control at
applied potentials of either 0.80 V or
1.00 V
At 90 C, (a) Constant voltage mode
(CVM), Upos = 1.0 V; (b) pulse voltage
mode (PVM), Upos = 1.0 V; (c) reverse
pulse voltage mode (RVM), Upos = 1.0 V,
Uneg = 1.0 Vtfwd = 2 s, trev = 1 s,Upos = 1.0
V, and Uneg = 1.0 V are adopted for the
RVM
1.2 V was applied between the working
and counter electrodes using a 12 V
power supply
[106]
[83]
[107]
[76]
[119]
At 35 3 C, at constant potential (1.0

V) electrodeposition duration 10 s, 30 s
and 60 s for Ni lm
At 70, 80 and 90 C, potential (1.0 V)
[120]

Cyclic voltammetry
system
At 25 3 C, working voltage: 1.0 V, for

60 min
At 70 C, 50 mV s1, electrodeposition
starts from 1.6 V, electrodeposition
starts from 1.6 V (negative-going
sweep)
[122]
Programmed
electrodeposition
method, threeelectrode system
At 80 C, potential step from 1.20 V (vs

Pt) to 1.50 V, and this potential was
maintained for 1 s to generate Pt nuclei.
The growth of the Pt nuclei into concave
tetrahexahedral (THH) Pt NCs was
achieved by applying a square-wave
potential (f = 10 Hz) with the lower (EL)
and upper (EU) potential limits of 1.30
and 0.30 V, respectively
[84]

Ag|AgCl/
NaCl 3 M
mounted in
a Luggin
capillary
containing
the DES
solvent
Pt quasireference
electrode
[82]
[121]
Nanomaterial
produced
Salt
[108]
(continued on next page)

561
562
Table 8 (continued)
DES type
Electrolyte composition
HBD
Molar
ratio
(Salt:HBD)
ChCl
Urea
1:2
10 mM K2PdCl4 DES
solution
ChCl
Urea
1:2
ChCl
Chromium chloride
CrCl36H2O
ChCl
Nanomaterial
produced
Electrochemical cell information
Electrodeposition
method
Electrodeposition conditions & remarks
Ref.
Ag/AgCl
minireference
electrode
(eDAQ)
Cyclic voltammetry
system
[109]
Ag quasireference
electrode
Galvanostatic, threeelectrode system
To deposit as many particles as possible,

the approximate cathodic limit of the
electrochemical window of the DES (at
32.5 C) was used (ca. 1.8 V). A lower
overpotential of 1.4 V was applied
during the growth pulse to minimize the
size dispersion of the particles two
different temperatures were used for
each electrodeposition sequence: 32.5
and 44.5 C
At 60 C, galvanostatically at a current
density of -2 mA/cm2 for 30 min and
constant agitation using a magnetic
stirrer (900 rpm)
At 20 C, in an open beaker, Currents of
no more than 0.15 A were used
The deposition current density was

3.0 mA/cm2 and deposition time was
60 min. The temperature was kept at
70 C
The DES medium was kept under
constant magnetic stirring in an
electrochemical cell of 10 ml capacity.
During the process, a mild gas evolution
was seen at the cathode in DES medium.
FOR Ag: at 50 C, current density
14 mA cm2, 30 min1 h
FOR Au: at 50 C, current density
0.3 A cm2 for a duration of 20 min
FOR Pd: at room temperature, current
density 1 A cm2 for 30 min
At variable applied voltages and ambient
temperature (25 3 C) without the
deaeration process
e.g. at 0.5 V, for 2 min and at 0.7 V for
5 min (200300 nm average size and
3040 nm pore size)
At 50 2 C current densities of
4 mA cm2, 6 mA cm2 and 8 mA cm2
Varied metal contents were dependent
on current density and electrolyte
composition
At 30 2 C starts at
0.520 V for electrolyte (a)
0.550 V for electrolyte (b)
0.600 V for electrolyte (c)
[81]
Anode (counter
electrode)
Cathode (working
electrode)
Reference
electrode
Pd nanoparticles
Pt
Glassy carbon foil
0.3 M NiCl2 in
DES + 0.1 g/L MWCNT
Ni/MWCNT
coating
Ni
1 cm2 Cu plate
1:2
DES
Nano-chromium
magnetic
domains
Platinised Ti
anode
Two-electrode system
Urea
1:2

NiCl26H2O
Ni
nanocrystalline
Two parallel Ni
plates
CNT growing on
substrates that
include titanium
nitride coated silicon
chips or polished
stainless steel
Mg3.0Nd0.2Zn
0.4Zr (wt.%, NZ30 K)
alloy
ChCl/ChCl
Urea/Ethylene glycol
1:2/1:2
Thin lms of
noble metallic
nanoparticles
such as Au, Ag
and Pd
FOR Ag: silver

wire (0.5 mm)
diameter
FOR Au: gold wire
(0.5 mm)
diameter
FOR Pd:Palladium
wire (0.5 mm)
diameter
FOR Ag: Pt/Rh (or W)

Wire
FOR Au: gold disc
1 mm diameter
Chronopotentiometric
mode / two-electrode
system / anodic
dissolution technique
ChCl
Ethylene glycol
1:2
FOR Ag: DES + 4Mercapto phenyl boronic

acid (MPBA, 5 mM)
stabilizer and sodium
borohydride (0.15 M
NaBH4) as a reducing
agent
FOR Au: DES + (0.15 M
NaBH4) as a reducing
agent
FOR Pd: DES
SnCl22H2O
Nanoporous thin
lm of Sn
Sn plate
Cu foil 0.03 mm

ChCl
Urea
1:2
Nanostructured
ZnNiP alloy
lm
Ni
Cu plate 20 50 mm
Ag quasireference
electrode
Three-electrode
system
ChCl
Ethylene glycol
1:2
Nanostructured
NiP alloy lm
Ni
Brass (CuZn alloy)
Ag quasireference
electrode
Cyclic voltammetry
system
ChCl
Ethylene glycol
1:2
Nanostructured
CoSn alloy lm
Sn plate
Cu foil (0.05 mm
thickness)
Ag wire
Three-electrode
system
DES containing:
(a) 0.4 M ZnCl20.1 M
NiCl20.05 M NH4H2PO2
or (b) 0.4 M ZnCl20.1 M
NiCl20.1 M NH4H2PO2
DES containing:
(a) 0.30 M NiCl26H2O
0.05 M NaH2PO2H2O
(b) NiCl26H2O0.1 M
NaH2PO2H2O
(c) NiCl26H2O0.15 M
NaH2PO2H2O
CoCl26H2O0.05 M
SnCl22H2O
Galvanostatic method
/ two-electrode system
At variable potentials (0.8 V, 1.0 V

and 1.2 V) and temperatures (75 C and
25 C)
Electrodeposition times varied to obtain
same electric quantity
[77]
[127]
[110]
[123]
[80]
[79]
[78]
Salt
563
Fig. 4. Cryo-TEM micrographs of gold nanoparticles in DES synthesized by sputter deposition at 20 mA and 0.05 mbar (argon pressure). (a and a0 ) 300 s without stabilizer
[68].
Fig. 5. SEM images of the pure PVDF lm (a) and the DES-NiCl2@PVDF lm (b). Inset of (b) is the corresponding magnied SEM picture [93].
Fig. 6. Schematic illustration of the synthetic procedure for the coreshell structured NiP nanoparticles [74].
crystalline NiP nanoparticles were produced in (ChCl:Ethylene

glycol) DES with coreshell structure. Fig. 6 illustrates the core
shell procedure to obtain NiP nanoparticles [74]. Fe2O3 nanospindles were also synthesized ionothermally in ChCl:U and showed a
high capacity, good cycle stability and rate performance for the
produced electrode in lithium ion battery [75].
Crystal growth mechanism was studied most often in every
ionothermal strategy. As each reported study represented a unique
reaction mechanism, no generalization can be conrmed. Fig. 7
summarizes some recent examples for the different mechanisms
suggested for ionothermal production of nanostructures.
Applications of electrochemically produced nanomaterials were
almost to fabricate protecting lms with high enhanced corrosion
resistance. This was reported for single metal coating (such as Ni
[76]) and multi-ingredient coating (such as Ni/MWCNT composite
[77], CoSn alloy [78], NiP alloy [79], ZnNiP [80] and MgNd
ZnZr alloy [81]). DES electrolytes have offered a exibility to
obtain several lm compositions for different coating purposes.
The key factor was to adjust the dosage between chemical components dissolved in DESs.
Catalytic activities of electrochemically produced nanoparticles
were also a matter of study for different reactions [8284]. Special
morphologies obtained were controllable by changing time, current density, temperature as well as the applied potential. This
helped to study the various activities obtained and helped to identify the growth mechanism of the produced particles.
However, the environmental aspects of DESs after being
employed were not assessed. This clearly shows the need of
environmental studies and studying the environmental impact of
DESs, for instance, handling DESs after nanoparticles preparation,
564
Fig. 7. Schematic illustrations for some suggested mechanisms to produce nanostructured materials ionothermally.
discharging them or using them in recycling processes. A few studies reported the successful recycling of DESs after using them as
media to disperse and produce nanoparticles and nanocomposites

[52,58,64,85,86].
2.3. Applications of nanosized DESs

DESs have taken a wide interest since they have been discovered. Many studies have emerged in an accelerating rate covering
the physical and chemical properties of these promising solvents
and proposing various applications in different eld of science.
As common with most studies, the basic concern on nanomaterial properties is placed on the solid phase only. Recently,
some reports have emerged and revealed novel physicochemical
properties of ILs and DESs which designed somehow to be in
nano-scale dimensions. Many techniques have been used to study
the liquid in such scales. For IL case in general, ILs nanostructures
can be formed (1) as nano-thick lms on a substrate surface [87],
(2) nanodroplet by immobilization in nanowells of mesoporous
materials [37] or by molecular beam deposition route [88], (3)
and as connement by conning the IL in nano-sized spaces of
nanomaterials such as the tubular space in CNT [89] or the narrow pores in nanoporous silica [90]. Connement is the most
reported case to study the physicochemical behavior of IL in
nano-volumes. It was also the rst route where DES has begun
to be studied in nano scales.
Chen et al. [91] used a SWCNT to conne a DES based on ChCl
and zinc chloride (1:1 M ratio) in an intriguing way. The procedure
for encapsulation involved thermal treatment of synthesized
SWCNT to remove end-caps, loading both SWCNTs and DES separately in H-type quartz tube, sealing the tube under vacuum
(107 torr) and then mixing at 200 C for 72 h. The morphology
and melting behavior of the encapsulated DES were studied using
different techniques such as high-resolution transmission electron microscopy (HRTEM) and in situ TEM electron beam irradiation. The results showed that the tube size play the main role in
morphology determination. With an increasing size of SWCNTs
diameter, a tendency was observed to form single-chain, double-helix, zigzag tube, and nally, random tube morphologies.
Thermal stability of the conned DES was found to be much higher
than in the bulk DES. These results and others aim to get further
understanding of the structure and phase behavior of nano-conned DESs and improve their use in solar cells, lubricants and
catalysts.
Thermochromic materials have a signicant role in built
environment. They are usually formed as crystalline or polymeric
solid or as solutions of transition metal complexes including the
solvent molecule as donor [92]. Gu and coworkers [93] discovered
that DESs with their solvolysis properties can be used to dissolve
metal complexes and enable thermochromism. Two types of
ChCl-based DESs (i.e. ChCl:U and ChCl:EG, 1:2 M ratios in both)
were used to dissolve different transition metal chlorides.
However, only NiCl26H2O exhibited a stable and prominent thermochromic behavior within a wide range of temperature from
room temperature to about 150 C. This was utilized to fabricate
a thermochromic poly(vinylidene uoride) (PVDF) composite lm
by embedding DESNiCl2 nanosized droplets in PVDF micropores
(Fig. 5). Color-temperature relation of the composite lm was fully
reversible owing to the uniformly dispersed nanodroplets on the
ligaments and channels of the porous structure.
3. Conclusion
This summarized the up-to-date studies of employing DESs in
diverse nanotechnology areas. The unique properties of DESs offer
them some advantages to in comparison to ILs. DESs have been
used as dispersants, exfoliating agents and templates for nanomaterials. Their application as media to synthesize nanoparticles
chemically, physically, physicochemically or electrochemically
resembles those for ILs. However, some positive features can be
565
added to DES use over ILs such as their easy preparation and being
much eco-friendlier. DESs like ILs can be obtained in nano-size
with many intriguing features, but these investigations are still
in their infancy compared to conventional ILs that have made great
strides in the eld of nano-environment. Various applications can
be predicted for DESs in the near future especially the ones
reported previously in IL area. Although there have been huge
efforts placed on studying ILs applications in nanotechnology, the
degree of DES contribution is still limited. Hence, it is highly
recommended to encourage research to follow up with the rest
of applications available from pre-established ones for ILs.
Investigations can be conducted not only by employing an
already-known or famous DES in particular, but also by designing
specic-task DESs based on available materials to be suited for
the desired application in nanotechnology.
Acknowledgments
The authors would like to express their thanks to University of
Malaya HIR-MOHE (D000003-16001) and University of Malaya
Centre for Ionic Liquids (UMCiL) for their support to this research.
References
[1] A.P. Abbott, G. Capper, D.L. Davies, R.K. Rasheed, V. Tambyrajah, Novel solvent
properties of choline chloride/urea mixtures, Chem. Commun. (2003) 7071.
[2] C. Atwater, Choline, Ullmanns Encyclopedia of Industrial Chemistry, WileyVCH Verlag GmbH & Co. KGaA2000.
[3] B. Tang, K. Row, Recent developments in deep eutectic solvents in chemical
sciences, Monatsh Chem. 144 (2013) 14271454.
[4] Z. Maugeri, P. Dominguez de Maria, Novel choline-chloride-based deepeutectic-solvents with renewable hydrogen bond donors: levulinic acid and
sugar-based polyols, RSC Adv. 2 (2012) 421425.
[5] A.P. Abbott, R.C. Harris, K.S. Ryder, C. DAgostino, L.F. Gladden, M.D. Mantle,
Glycerol eutectics as sustainable solvent systems, Green Chem. 13 (2011) 82
90.
[6] A.P. Abbott, D. Boothby, G. Capper, D.L. Davies, R.K. Rasheed, Deep eutectic
solvents formed between choline chloride and carboxylic acids: versatile
alternatives to ionic liquids, J. Am. Chem. Soc. 126 (2004) 91429147.
[7] Ru, B. Konig, Low melting mixtures in organic synthesis an alternative to
ionic liquids?, Green Chem 14 (2012) 29692982.
[8] A.P. Abbott, G. Capper, K.J. McKenzie, K.S. Ryder, Electrodeposition of zinctin
alloys from deep eutectic solvents based on choline chloride, J. Electroanal.
Chem. 599 (2007) 288294.
[9] A.P. Abbott, J. Grifth, S. Nandhra, C. OConnor, S. Postlethwaite, K.S. Ryder,
E.L. Smith, Sustained electroless deposition of metallic silver from a choline
chloride-based ionic liquid, Surf. Coat. Technol. 202 (2008) 20332039.
[10] P. Domnguez de Mara, Z. Maugeri, Ionic liquids in biotransformations: from
proof-of-concept to emerging deep-eutectic-solvents, Curr. Opin. Chem. Biol.
15 (2011) 220225.
[11] T. Welton, Room-temperature ionic liquids. Solvents for synthesis and
catalysis, Chem. Rev. 99 (1999) 20712084.
[12] M.G. Del Ppolo, G.A. Voth, On the structure and dynamics of ionic liquids, J.
Phys. Chem. B 108 (2004) 17441752.
[13] D. Carriazo, M.C. Serrano, M.C. Gutierrez, M.L. Ferrer, F. del Monte, Deepeutectic solvents playing multiple roles in the synthesis of polymers and
related materials, Chem. Soc. Rev. 41 (2012) 49965014.
[14] D. Lloyd, T. Vainikka, M. Ronkainen, K. Kontturi, Characterisation and
application of the Fe(II)/Fe(III) redox reaction in an ionic liquid analogue,
Electrochim. Acta 109 (2013) 843851.
[15] M. Cvjetko Bubalo, K. Radoevic, I. Radojcic Redovnikovic, J. Halambek, V.
Gaurina Srcek, A brief overview of the potential environmental hazards of
ionic liquids, Ecotoxicol. Environ. Saf. 99 (2014) 112.
[16] S. Tang, G.A. Baker, H. Zhao, Ether- and alcohol-functionalized task-specic
ionic liquids: attractive properties and applications, Chem. Soc. Rev. 41
(2012) 40304066.
[17] Q. Zhang, K. De Oliveira Vigier, S. Royer, F. Jerome, Deep eutectic solvents:
syntheses, properties and applications, Chem. Soc. Rev. 41 (2012) 71087146.
[18] A.P. Abbott, G. Capper, D.L. Davies, K.J. McKenzie, S.U. Obi, Solubility of metal
oxides in deep eutectic solvents based on choline chloride, J. Chem. Eng. Data
51 (2006) 12801282.
[19] C.A. Nkuku, R.J. LeSuer, Electrochemistry in deep eutectic solvents, J. Phys.
Chem. B 111 (2007) 1327113277.
[20] M.H. Chakrabarti, F.S. Mjalli, I.M. AlNashef, M.A. Hashim, M.A. Hussain, L.
Bahadori, C.T.J. Low, Prospects of applying ionic liquids and deep eutectic
solvents for renewable energy storage by means of redox ow batteries,
Renew. Sust. Energy Rev. 30 (2014) 254270.
[21] P. Wasserscheid, T. Welton, Ionic Liquids in Synthesis, Wiley Online Library,
2008.
566
[22] Y.-J. Ju, C.-H. Lien, K.-H. Chang, C.-C. Hu, D.S.-H. Wong, Deep eutectic solventbased ionic liquid electrolytes for electrical double-layer capacitors, J. Chin.
Chem. Soc. 59 (2012) 12801287.
[23] X. Baokou, M. Anouti, Physical properties of a new deep eutectic solvent
based on a sulfonium ionic liquid as a suitable electrolyte for electric doublelayer capacitors, J. Phys. Chem. C 119 (2014) 970979.
[24] A.P. Abbott, G. Capper, D.L. Davies, R.K. Rasheed, Ionic liquid analogues
formed from hydrated metal salts, Chem. A Eur. J. 10 (2004) 37693774.
[25] H. Zhao, G.A. Baker, S. Holmes, New eutectic ionic liquids for lipase activation
and enzymatic preparation of biodiesel, Org. Biomol. Chem. 9 (2011) 1908
1916.
[26] E.L. Smith, A.P. Abbott, K.S. Ryder, Deep eutectic solvents (DESs) and their
applications, Chem. Rev. 114 (2014) 1106011082.
[27] M.C. Buzzeo, R.G. Evans, R.G. Compton, Non-haloaluminate roomtemperature ionic liquids in electrochemistrya review, ChemPhysChem 5
(2004) 11061120.
[28] S. Zhang, N. Sun, X. He, X. Lu, X. Zhang, Physical properties of ionic liquids:
database and evaluation, J. Phys. Chem. Ref. Data 35 (2006) 14751517.
[29] J.L. Anthony, J.F. Brennecke, J.D. Holbrey, E.J. Maginn, R.A. Mantz, R.D. Rogers,
P.C. Trulove, A.E. Visser, T. Welton, Physicochemical Properties of Ionic
Liquids, Ionic Liquids in Synthesis, Wiley-VCH Verlag GmbH & Co. KGaA2003,
pp. 41126.
[30] Y.H. You, C.D. Gu, X.L. Wang, J.P. Tu, Electrodeposition of NiCo alloys from a
deep eutectic solvent, Surf. Coat. Technol. 206 (2012) 36323638.
[31] A.P. Abbott, J.C. Barron, G. Frisch, S. Gurman, K.S. Ryder, A. Fernando Silva,
Double layer effects on metal nucleation in deep eutectic solvents, Phys.
Chem. Chem. Phys. 13 (2011) 1022410231.
[32] F.S. Ghareh Bagh, F.S. Mjalli, M.A. Hashim, M.K.O. Hadj-Kali, I.M. AlNashef,
Solubility of sodium salts in ammonium-based deep eutectic solvents, J.
Chem. Eng. Data 58 (2013) 21542162.
[33] R.R. Deshmukh, R. Rajagopal, K.V. Srinivasan, Ultrasound promoted CC bond
formation: Heck reaction at ambient conditions in room temperature ionic
liquids, Chem. Commun. (2001) 15441545.
[34] N.L. Mai, K. Ahn, Y.-M. Koo, Methods for recovery of ionic liquids a review,
Process. Biochem. 49 (2014) 872881.
[35] A.K. Gupta, Y.L. Verma, R.K. Singh, S. Chandra, Studies on an ionic liquid
conned in silica nano pores: change in Tg and evidence of organic-inorganic
linkage at the pore wall surface, J. Phys. Chem. C 118 (2013) 15301539.
[36] F. Shi, Y. Deng, Abnormal FT-IR and FT Raman spectra of ionic liquids conned
in nano-porous silica gel, Spectrochim. Acta Mol. Biomol. Spectros. 62 (2005)
239244.
[37] Y. Mo, J. Pu, F. Huang, Dynamic forces of ionic liquid nano-droplets measured
by atomic force microscope, Colloids Surf. A 429 (2013) 1923.
[38] A.M. Smith, K.R.J. Lovelock, S. Perkin, Monolayer and bilayer structures in
ionic liquids and their mixtures conned to nano-lms, Faraday Discuss. 167
(2013) 279292.
[39] A.R. Petosa, D.P. Jaisi, I.R. Quevedo, M. Elimelech, N. Tufenkji, Aggregation and
deposition of engineered nanomaterials in aquatic environments: role of
physicochemical interactions, Environ. Sci. Technol. 44 (2010) 65326549.
[40] R. Saidur, K.Y. Leong, H.A. Mohammad, A review on applications and
challenges of nanouids, Renew. Sust. Energy Rev. 15 (2011) 16461668.
[41] M.L. Polo-Luque, B.M. Simonet, M. Valcrcel, Functionalization and dispersion of
carbon nanotubes in ionic liquids, TrAC, Trends Anal. Chem. 47 (2013) 99110.
[42] C. Reichardt, Solvents and Solvent Effects in Organic Chemistry, Wiley-VCH
Verlag GmbH & Co. KGaA2004.
[43] Y. Zhou, M. Antonietti, Synthesis of very small TiO2 nanocrystals in a roomtemperature ionic liquid and their self-assembly toward mesoporous
spherical aggregates, J. Am. Chem. Soc. 125 (2003) 1496014961.
[44] D.V. Wagle, H. Zhao, G.A. Baker, Deep eutectic solvents: sustainable media for
nanoscale and functional materials, Acc. Chem. Res. 47 (2014) 22992308.
[45] C. Janiak, Metal Nanoparticle Synthesis in Ionic Liquids, Springer, Berlin,
Heidelberg, 2014. pp. 137.
[46] A. Wittmar, M. Ulbricht, Dispersions of various titania nanoparticles in two
different ionic liquids, Ind. Eng. Chem. Res. 51 (2012) 84258433.
[47] Q. Ji, S. Acharya, G.J. Richards, S. Zhang, J. Vieaud, J.P. Hill, K. Ariga, Alkyl
imidazolium
ionic-liquid-mediated
formation
of
gold
particle
superstructures, Langmuir 29 (2013) 71867194.
[48] S. Javadian, V. Ruhi, A. Asadzadeh Shahir, A. Heydari, J. Akbari, Imidazoliumbased ionic liquids as modulators of physicochemical properties and
nanostructures of ctab in aqueous solution: the effect of alkyl chain length,
hydrogen bonding capacity, and anion type, Ind. Eng. Chem. Res. 52 (2013)
1583815846.
[49] J.-H. Oh, J.-S. Lee, Synthesis of gold microstructures with surface
nanoroughness using a deep eutectic solvent for catalytic and diagnostic
applications, J. Nanosci. Nanotechnol. 14 (2014) 37533757.
[50] N. Liu, X. Chen, Z. Ma, Ionic liquid functionalized graphene/Au
nanocomposites and its application for electrochemical immunosensor,
Biosens. Bioelectron. 48 (2013) 3338.
[51] S. Vadahanambi, J.-H. Jung, R. Kumar, H.-J. Kim, I.-K. Oh, An ionic liquidassisted method for splitting carbon nanotubes to produce graphene nanoribbons by microwave radiation, Carbon 53 (2013) 391398.
[52] D. Mondal, J. Bhatt, M. Sharma, S. Chatterjee, K. Prasad, A facile approach to
prepare a dual functionalized DNA based material in a bio-deep eutectic
solvent, Chem. Commun. 50 (2014) 39893992.
[53] E. Commission, Recommendation on the Denition of a Nanomaterial, 2011.
[54] S. Park, R.S. Ruoff, Chemical methods for the production of graphenes, Nat.
Nanotechnol. 4 (2009) 217224.
[55] M. Cai, D. Thorpe, D.H. Adamson, H.C. Schniepp, Methods of graphite
exfoliation, J. Mater. Chem. 22 (2012) 2499225002.
[56] Chapter 1 Carbon Nanotubes, Nanotubes and Nanowires (2), The Royal
Society of Chemistry 2011, pp. 1242.
[57] R.A. Boulos, E. Eroglu, X. Chen, A. Scafdi, B.R. Edwards, J. Toster, C.L. Raston,
Unravelling the structure and function of human hair, Green Chem. 15 (2013)
12681273.
[58] M.C. Gutirrez, D. Carriazo, A. Tamayo, R. Jimnez, F. Pic, J.M. Rojo, M.L.
Ferrer, F. del Monte, Deep-eutectic-solvent-assisted synthesis of hierarchical
carbon electrodes exhibiting capacitance retention at high current densities,
Chem. Eur. J. 17 (2011) 1053310537.
[59] M. Galinski, A. Lewandowski, I. Stepniak, Ionic liquids as electrolytes,
[60] B. Garcia, S. Lavalle, G. Perron, C. Michot, M. Armand, Room temperature molten
salts as lithium battery electrolyte, Electrochim. Acta 49 (2004) 45834588.
[61] R. Ktz, M. Carlen, Principles and applications of electrochemical capacitors,
[62] A. Lewandowski, A. Swiderska-Mocek, Ionic liquids as electrolytes for Li-ion
batteries an overview of electrochemical studies, J. Power Sources 194
(2009) 601609.
[63] Y. Zheng, L. Ye, L. Yan, Y. Gao, The electrochemical behavior and
determination of quercetin in choline chloride/urea deep eutectic solvent
electrolyte based on abrasively immobilized multi-wall carbon nanotubes
modied electrode, Int. J. Electrochem. Sci. 9 (2014).
[64] J. Lu, X.-T. Li, E.-Q. Ma, L.-P. Mo, Z.-H. Zhang, Superparamagnetic CuFeO2
nanoparticles in deep eutectic solvent: an efcient and recyclable catalytic
system for the synthesis of imidazo[1,2-a]pyridines, ChemCatChem 6 (2014)
28542859.
[65] T. Welton, F. Endres, S.Z.E. Abedin, M. Antonietti, B. Smarsly, Y. Zhou,
Inorganic Synthesis, Ionic Liquids in Synthesis, Wiley-VCH Verlag GmbH & Co.
KGaA2008, pp. 569617.
[66] D. Bera, S. Kuiry, S. Seal, Synthesis of nanostructured materials using
template-assisted electrodeposition, JOM 56 (2004) 4953.
[67] V.S. Raghuwanshi, M. Ochmann, A. Hoell, F. Polzer, K. Rademann, Deep
eutectic solvents for the self-assembly of gold nanoparticles: A SAXS, UVVis,
and TEM investigation, Langmuir 30 (2014) 60386046.
[68] V.S. Raghuwanshi, M. Ochmann, F. Polzer, A. Hoell, K. Rademann, Selfassembly of gold nanoparticles on deep eutectic solvent (DES) surfaces,
Chem. Commun. 50 (2014) 86938696.
[69] Y. Zhao, Y. Zhao, H. Feng, J. Shen, Synthesis of nickel phosphide nano-particles
in a eutectic mixture for hydrotreating reactions, J. Mater. Chem. 21 (2011)
81378145.
[70] X. Ge, C.D. Gu, X.L. Wang, J.P. Tu, Endowing manganese oxide with fast
adsorption ability through controlling the manganese carbonate precursor
assembled in ionic liquid, J. Colloid Interface Sci. 438 (2015) 149158.
[71] X. Ge, C.D. Gu, X.L. Wang, J.P. Tu, Anomalous self-reduction of layered double
hydroxide (LDH): from [small alpha]-Ni(OH)2 to hexagonal close packing
(HCP) Ni/NiO by annealing without a reductant, Chem. Commun. 51 (2015)
10041007.
[72] X. Ge, C.D. Gu, X.L. Wang, J.P. Tu, Ionothermal synthesis of cobalt iron layered
double hydroxides (LDHs) with expanded interlayer spacing as advanced
electrochemical materials, J. Mater. Chem. A 2 (2014) 1706617076.
[73] X. Ge, C.D. Gu, X.L. Wang, J.P. Tu, Correlation between microstructure and
electrochemical behavior of the mesoporous Co3O4 sheet and its ionothermal
synthesized hydrotalcite-like a-Co(OH)2 precursor, J. Phys. Chem. C 118
(2013) 911923.
[74] H. Zhang, Y. Lu, C.-D. Gu, X.-L. Wang, J.-P. Tu, Ionothermal synthesis and
lithium storage performance of core/shell structured amorphous@crystalline
NiP nanoparticles, CrystEngComm 14 (2012) 79427950.
[75] Q.Q. Xiong, J.P. Tu, X. Ge, X.L. Wang, C.D. Gu, One-step synthesis of hematite
nanospindles from choline chloride/urea deep eutectic solvent with highly
powerful storage versus lithium, J. Power Sources.
[76] C. Gu, J. Tu, One-step fabrication of nanostructured Ni lm with lotus effect
from deep eutectic solvent, Langmuir 27 (2011) 1013210140.
[77] P. Martis, V.S. Dilimon, J. Delhalle, Z. Mekhalif, Electro-generated
nickel/carbon nanotube composites in ionic liquid, Electrochim. Acta 55
(2010) 54075410.
[78] J.L. Zhang, C.D. Gu, S. Fashu, Y.Y. Tong, M.L. Huang, X.L. Wang, J.P. Tu,
Enhanced corrosion resistance of CoSn alloy coating with a self-organized
layered structure electrodeposited from deep eutectic solvent, J. Electrochem.
Soc. 162 (2015) D1D8.
[79] Y. You, C. Gu, X. Wang, J. Tu, Electrochemical synthesis and characterization
of NiP alloy coatings from eutectic-based ionic liquid, J. Electrochem. Soc.
159 (2012) D642D648.
[80] S. Fashu, C.D. Gu, X.L. Wang, J.P. Tu, Structure, composition and corrosion
resistance of ZnNiP alloys electrodeposited from an ionic liquid based on
choline chloride, J. Electrochem. Soc. 161 (2014) D3011D3017.
[81] X. Guo, S. Wang, J. Gong, J. Guo, L. Peng, W. Ding, Characterization of highly
corrosion-resistant nanocrystalline Ni coating electrodeposited on MgNd
ZnZr alloy from a eutectic-based ionic liquid, Appl. Surf. Sci. 313 (2014)
711719.
[82] L. Wei, Y.-J. Fan, H.-H. Wang, N. Tian, Z.-Y. Zhou, S.-G. Sun, Electrochemically
shape-controlled synthesis in deep eutectic solvents of Pt nanoowers with
[83]
[84]
[85]
[86]
[87]
[88]
[89]
[90]
[91]
[92]
[93]
[94]
[95]
[96]
[97]
[98]
[99]
[100]
[101]
[102]
[103]
[104]
[105]
enhanced activity for ethanol oxidation, Electrochim. Acta 76 (2012) 468

474.
L. Wei, Z.-Y. Zhou, S.-P. Chen, C.-D. Xu, D. Su, M.E. Schuster, S.-G. Sun,
Electrochemically shape-controlled synthesis in deep eutectic solvents:
triambic icosahedral platinum nanocrystals with high-index facets and
their enhanced catalytic activity, Chem. Commun. 49 (2013) 1115211154.
L. Wei, Y.-J. Fan, N. Tian, Z.-Y. Zhou, X.-Q. Zhao, B.-W. Mao, S.-G. Sun,
Electrochemically shape-controlled synthesis in deep eutectic solvents a
new route to prepare Pt nanocrystals enclosed by high-index facets with high
catalytic activity, J. Phys. Chem. C 116 (2011) 20402044.
J.D. Mota-Morales, M.C. Gutierrez, M.L. Ferrer, R. Jimenez, P. Santiago, I.C.
Sanchez, M. Terrones, F. Del Monte, G. Luna-Barcenas, Synthesis of
macroporous poly(acrylic acid)-carbon nanotube composites by frontal
polymerization in deep-eutectic solvents, J. Mater. Chem. A 1 (2013) 3970
3976.
C. Mukesh, D. Mondal, M. Sharma, K. Prasad, Choline chloridethiourea, a
deep eutectic solvent for the production of chitin nanobers, Carbohydr.
Polym. 103 (2014) 466471.
Z. Wang, C. Priest, Impact of nanoscale surface heterogeneity on precursor
lm growth and macroscopic spreading of [Rmim][NTf2] ionic liquids on
mica, Langmuir 29 (2013) 1134411353.
S. Maruyama, Y. Takeyama, H. Taniguchi, H. Fukumoto, M. Itoh, H.
Kumigashira, M. Oshima, T. Yamamoto, Y. Matsumoto, Molecular beam
deposition of nanoscale ionic liquids in ultrahigh vacuum, ACS Nano 4 (2010)
59465952.
S. Chen, H.E. Lim, Y. Miyata, R. Kitaura, Y. Bando, D. Golberg, H. Shinohara,
Transformation of ionic liquid into carbon nanotubes in conned nanospace,
Chem. Commun. 47 (2011) 1036810370.
F. Shi, Q. Zhang, D. Li, Y. Deng, Silica-gel-conned ionic liquids: a new attempt
for the development of supported nanoliquid catalysis, Chem. Eur. J. 11
(2005) 52795288.
S. Chen, K. Kobayashi, Y. Miyata, N. Imazu, T. Saito, R. Kitaura, H. Shinohara,
Morphology and melting behavior of ionic liquids inside single-walled carbon
nanotubes, J. Am. Chem. Soc. 131 (2009) 1485014856.
X. Wei, L. Yu, X. Jin, D. Wang, G.Z. Chen, Solar-thermochromism of
pseudocrystalline nanodroplets of ionic liquid-NiII complexes immobilized
inside translucent microporous PVDF lms, Adv. Mater. 21 (2009) 776780.
C.-D. Gu, J.-P. Tu, Thermochromic behavior of chloro-nickel(II) in deep
eutectic solvents and their application in thermochromic composite lms,
RSC Adv. 1 (2011) 12201227.
X. Ge, C.D. Gu, Y. Lu, X.L. Wang, J.P. Tu, A versatile protocol for the
ionothermal synthesis of nanostructured nickel compounds as energy storage
materials from a choline chloride-based ionic liquid, J. Mater. Chem. A 1
(2013) 1345413461.
C. DAgostino, R.C. Harris, A.P. Abbott, L.F. Gladden, M.D. Mantle, Molecular
motion and ion diffusion in choline chloride based deep eutectic solvents
studied by 1H pulsed eld gradient NMR spectroscopy, Phys. Chem. Chem.
Phys. 13 (2011) 2138321391.
A.P. Abbott, G. Capper, S. Gray, Design of improved deep eutectic solvents
using hole theory, ChemPhysChem 7 (2006) 803806.
A.P. Abbott, J.C. Barron, K.S. Ryder, D. Wilson, Eutectic-based ionic liquids
with metal-containing anions and cations, Chem. A Eur. J. 13 (2007) 6495
6501.
K. Shahbaz, S. Baroutian, F.S. Mjalli, M.A. Hashim, I.M. AlNashef, Densities of
ammonium and phosphonium based deep eutectic solvents: prediction using
articial intelligence and group contribution techniques, Thermochim. Acta
527 (2012) 5966.
K. Shahbaz, F.S. Mjalli, M.A. Hashim, I.M. AlNashef, Prediction of the surface
tension of deep eutectic solvents, Fluid Phase Equilibria 319 (2012) 4854.
A.P. Abbott, R.C. Harris, K.S. Ryder, Application of hole theory to dene ionic
liquids by their transport properties, J. Phys. Chem. B 111 (2007) 4910
4913.
J.D. Mota-Morales, M.C. Gutierrez, I.C. Sanchez, G. Luna-Barcenas, F. del
Monte, Frontal polymerizations carried out in deep-eutectic mixtures
providing both the monomers and the polymerization medium, Chem.
Commun. 47 (2011) 53285330.
A.P. Abbott, G. Capper, D.L. Davies, R. Rasheed, Ionic liquids based upon metal
halide/substituted quaternary ammonium salt mixtures, Inorg. Chem. 43
(2004) 34473452.
M.A. Kareem, F.S. Mjalli, M.A. Hashim, I.M. AlNashef, Phosphonium-based
ionic liquids analogues and their physical properties, J. Chem. Eng. Data 55
(2010) 46324637.
K. Shahbaz, F.S. Mjalli, M.A. Hashim, I.M. AlNashef, Using deep eutectic
solvents based on methyl triphenyl phosphunium bromide for the removal of
glycerol from palm-oil-based biodiesel, Energy Fuels 25 (2011) 26712678.
F.S.G. Bagh, K. Shahbaz, F.S. Mjalli, I.M. AlNashef, M.A. Hashim, Electrical
conductivity of ammonium and phosphonium based deep eutectic solvents:
measurements and articial intelligence-based prediction, Fluid Phase
Equilib. 356 (2013) 3037.
567
[106] R. Bck, G. Lanzinger, R. Freudenberger, T. Mehner, D. Nickel, I. Scharf, T.

Lampke, Effect of additive and current mode on surface morphology of
palladium lms from a non-aqueous deep eutectic solution (DES), J. Appl.
Electrochem. 43 (2013) 12071216.
[107] A.P. Abbott, K. El Ttaib, G. Frisch, K.J. McKenzie, K.S. Ryder, Electrodeposition
of copper composites from deep eutectic solvents based on choline chloride,
Phys. Chem. Chem. Phys. 11 (2009) 42694277.
[108] E. Gomez, E. Valles, P. Cojocaru, A. Raygani, L. Magagnin, Electrodeposition of
SmCo nanostructures in deep eutectic solvent, ECS Trans. 41 (2012) 39.
[109] J.A. Hammons, T. Muselle, J. Ustarroz, M. Tzedaki, M. Raes, A. Hubin, H.
Terryn, Stability, assembly, and particle/solvent interactions of Pd
nanoparticles electrodeposited from a deep eutectic solvent, J. Phys. Chem.
C 117 (2013) 1438114389.
[110] A. Renjith, A. Roy, V. Lakshminarayanan, In situ fabrication of
electrochemically grown mesoporous metallic thin lms by anodic
dissolution in deep eutectic solvents, J. Colloid Interface Sci. 426 (2014)
270279.
[111] F. Chen, S. Xie, J. Zhang, R. Liu, Synthesis of spherical Fe3O4 magnetic
nanoparticles by co-precipitation in choline chloride/urea deep eutectic
solvent, Mater. Lett. 112 (2013) 177179.
[112] Y. Huang, F. Shen, J. La, G. Luo, J. Lai, C. Liu, G. Chu, Synthesis and
characterization of CuCl nanoparticles in deep eutectic solvents, Part. Sci.
Technol. 31 (2012) 8184.
[113] H.-G. Liao, Y.-X. Jiang, Z.-Y. Zhou, S.-P. Chen, S.-G. Sun, Shape-controlled
synthesis of gold nanoparticles in deep eutectic solvents for studies of
structure-functionality relationships in electrocatalysis, Angew. Chem. Int.
Ed. Engl. 47 (2008) 91009103.
[114] H. Zheng, C.-D. Gu, X.-L. Wang, J.-P. Tu, Fast synthesis and optical property of
SnO nanoparticles from choline chloride-based ionic liquid, J. Nanopart. Res.
16 (2014) 19.
[115] A. Querejeta-Fernndez, J.C. Hernndez-Garrido, H. Yang, Y. Zhou, A. Varela,
M. Parras, J.J. Calvino-Gmez, J.M. Gonzlez-Calbet, P.F. Green, N.A. Kotov,
Unknown aspects of self-assembly of PbS microscale superstructures, ACS
Nano 6 (2012) 38003812.
[116] Y.-H. Lu, W.-H. Lin, C.-Y. Yang, Y.-H. Chiu, Y.-C. Pu, M.-H. Lee, Y.-C. Tseng, Y.-J.
Hsu, A facile green antisolvent approach to Cu2+-doped ZnO nanocrystals
with visible-light-responsive photo activities, Nanoscale 6 (2014) 8796
8803.
[117] C.D. Gu, M.L. Huang, X. Ge, H. Zheng, X.L. Wang, J.P. Tu, NiO electrode for
methanol electro-oxidation: Mesoporous vs. nanoparticulate, Int. J. Hydrogen
Energy 39 (2014) 1089210901.
[118] Q. Sheng, R. Liu, J. Zheng, Prussian blue nanospheres synthesized in deep
eutectic solvents, Nanoscale 4 (2012) 68806886.
[119] A.P. Abbott, K.E. Ttaib, G. Frisch, K.S. Ryder, D. Weston, The electrodeposition
of silver composites using deep eutectic solvents, Phys. Chem. Chem. Phys. 14
(2012) 24432449.
[120] G.F. Cai, C.D. Gu, J. Zhang, P.C. Liu, X.L. Wang, Y.H. You, J.P. Tu, Ultra fast
electrochromic switching of nanostructured NiO lms electrodeposited from
choline chloride-based ionic liquid, Electrochim. Acta 87 (2013) 341347.
[121] G.-F. Cai, J.-P. Tu, C.-D. Gu, J.-H. Zhang, J. Chen, D. Zhou, S.-J. Shi, X.-L. Wang,
One-step fabrication of nanostructured NiO lms from deep eutectic solvent
with enhanced electrochromic performance, J. Mater. Chem. A 1 (2013)
42864292.
[122] C.D. Gu, Y.H. You, Y.L. Yu, S.X. Qu, J.P. Tu, Microstructure, nanoindentation,
and electrochemical properties of the nanocrystalline nickel lm
electrodeposited from choline chlorideethylene glycol, Surf. Coat. Technol.
205 (2011) 49284933.
[123] C.D. Gu, Y.J. Mai, J.P. Zhou, Y.H. You, J.P. Tu, Non-aqueous electrodeposition of
porous tin-based lm as an anode for lithium-ion battery, J. Power Sources
214 (2012) 200207.
[124] C. Gu, Y. Mai, J. Zhou, J. Tu, SnO2 nanocrystallite: novel synthetic route from
deep eutectic solvent and lithium storage performance, Funct. Mater. Lett. 4
(2011) 377381.
[125] C. Gu, H. Zhang, X. Wang, J. Tu, One-pot synthesis of SnO2/reduced graphene
oxide nanocomposite in ionic liquid-based solution and its application for
lithium ion batteries, Mater. Res. Bull. 48 (2013) 41124117.
[126] C.D. Gu, X.J. Xu, J.P. Tu, Fabrication and wettability of nanoporous silver lm
on copper from choline chloride-based deep eutectic solvents, J. Phys. Chem.
C 114 (2010) 1361413619.
[127] A.C. Wright, M.K. Faulkner, R.C. Harris, A. Goddard, A.P. Abbott,
Nanomagnetic domains of chromium deposited on vertically-aligned
carbon nanotubes, J. Magn. Magn. Mater. 324 (2012) 41704174.
[128] H. Maka, T. Spychaj, K. Kowalczyk, Imidazolium and deep eutectic ionic
liquids as epoxy resin crosslinkers and graphite nanoplatelets dispersants, J.
Appl. Polym. Sci. 131 (2014) 40401. doi: 40410.41002/APP.40401.
[129] S. Shahidi, S. Iranpour, P. Iranpour, A.A. Alavi, F.A. Mahyari, M. Tohidi, A.
Safavi, A new X-ray contrast agent based on highly stable gum arabic-gold
nanoparticles synthesised in deep eutectic solvent, J. Exp. Nanosci. (2014)
114.

Potential Applications of Deep Eutectic Solvents in Nanotechnology

Diunggah oleh

Informasi Dokumen

Hak Cipta

Format Tersedia

Bagikan dokumen Ini

Bagikan atau Tanam Dokumen

Opsi Berbagi

Apakah menurut Anda dokumen ini bermanfaat?

Apakah konten ini tidak pantas?

Hak Cipta:

Format Tersedia

Potential Applications of Deep Eutectic Solvents in Nanotechnology

Diunggah oleh

Hak Cipta:

Format Tersedia

Chemical Engineering Journal 273 (2015) 551567

Contents lists available at ScienceDirect

Chemical Engineering Journal

Potential applications of deep eutectic solvents in nanotechnology

DESs can play a primary role in

contribution in nanotechnology were

A. Abo-Hamad et al. / Chemical Engineering Journal 273 (2015) 551567

Media to disperse nanoparticles and control morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

melting point range of ILs, they can be described either as room

A. Abo-Hamad et al. / Chemical Engineering Journal 273 (2015) 551567

Conductivity (mS cm1)

ChCl:Urea (1:2 M ratio)

explore the mechanisms of electron-transfer reaction [19]. DESs

DES 1:ChCl:Malonic acid (1:1 M ratio).

in the rst place, therefore, temperature is also as important to

A. Abo-Hamad et al. / Chemical Engineering Journal 273 (2015) 551567

Examples for electrical conductivities of some common DESs,

1.3.2. Solvation properties

ILs & Nanotechnology

2. Main applications of DESs in nanotechnology

DESs & Nanotechnology Arcles

A. Abo-Hamad et al. / Chemical Engineering Journal 273 (2015) 551567

Electrolyte (nanostructure sensor)

2.1. Media to disperse nanoparticles and control morphology

A. Abo-Hamad et al. / Chemical Engineering Journal 273 (2015) 551567

Remarks & details

DES is polymerizable solvent helped to disperse

Type of HBD (component 2)

SiC and Al2O3

disperse nanoparticles during their preparation even it is for

A. Abo-Hamad et al. / Chemical Engineering Journal 273 (2015) 551567

carbon monoliths including MWCNTs. Researchers found that the

electrochemically, (3) photochemically, (4) sonochemically (using

Macroporous poly(acrylic acid)CNT

DES with ethylene glycol

At room temperature (25 3 C)

1st Step: 600 rpm and 80 C for 20 min

1st Step: stirring at 80 C

For Ni(NH3)Cl2 and nanosheet-like NiCl: Teon

At 323 K in N2 for 30 min

2nd Step: ultrasonically (200 W) for about 4 h

Spherical Fe3O4 magnetic

PbS nano/micro superstructures

SnO2/reduced graphene oxide

1st Step: 2.164 g (8 mmol) of FeCl3.6H2O

(14 mL) DES containing

A. Abo-Hamad et al. / Chemical Engineering Journal 273 (2015) 551567

Reaction medium and composition

Stirring at 500 rpm at 100 C for 2 h

DES with 10%, w/w Pure chitin powder

25 mL DES + L-ascorbic acid (0.05 g) +

nano-sized SnO crystals

At 100 C with a heating rate of 5 C.min1 under

Continuous stirring under ambient conditions

50 mL 0.1 M NiCl2/DES in a three-neck ask

Cu -doped ZnO nanocrystals

gum Arabic coated gold nanoparticles

Gold Microstructures with Surface

200lL (0.15 M) HAuCl4 + 20 mL of

0.1 M FeCl36H2O in DES

Ni layered double hydroxide (Ni LDH)

0.1 M NiCl2 in DES

Co Fe layered double hydroxide (CoFe

0.1 M Co+2 and 0.035 M Fe+3 in DES from