Nanotechnol Rev 2017; 6(3): 271–278

Future of nanotechnology contribution

Jae-Seung Lee*

Deep eutectic solvents as versatile media for the

synthesis of noble metal nanomaterials
DOI 10.1515/ntrev-2016-0106
Received December 8, 2016; accepted February 6, 2017; previously
published online March 20, 2017
Abstract: Deep eutectic solvents (DESs) were developed
15  years ago and have been used for various purposes
based on their unique chemical and physical properties.
Recently, they have been highlighted as versatile media
for the synthesis of noble metal nanomaterials. Although
there are a few limitations, their vast chemical library of
hydrogen bond donors and excellent solubility show great
potential for their future applications for the synthesis of
noble metal nanoparticles.
Keywords: deep eutectic solvent; gold; nanomaterial;
nanoparticle; silver.
because of their low vapor pressure, low cost, non-flam-
mability, and easy preparation. The global electroplating
market was estimated to be approximately 14.5 billion US$
in 2016 and is expected to continue expanding, indicating
the potential importance of DESs in industry [5]. In addi-
tion to metal processing, there is also a growing interest
in utilizing DESs as tunable media for organic chemical
syntheses, polymerization, and organic extraction and
separation [6, 7]. Theoretically, an unlimited number of
possible combinations of halide salts and HBDs (Figure 1)
could be used to design a DES, resulting in a large number
of suitable media for such inorganic and organic reactions.
It has also been demonstrated that DESs play a sig-
nificant role in the synthesis and fabrication of various
nanomaterials, such as zeolite analogs [8], carbon nano-
materials [9, 10], micro- and nanostructured semicon-
ductors [11–13], and DNA nanostructures [14]. As a result,

1 Introduction DESs have proved to be versatile media for nanoscale syn-

thesis based on their advantageous chemical and physical
properties [15, 16]. Despite the widespread impact of DESs,
Deep eutectic solvents (DESs) are an emerging class of
however, their role in the synthesis of noble metal nano-
low-transition-temperature mixtures (LTTMs), which are
materials, particularly gold and silver nanomaterials, has
liquids formed by hydrogen-bonding interactions of mul-
been rarely reported and discussed to date [17]. Consider-
tiple starting materials having higher melting tempera-
ing the importance of noble metal nanomaterials in nano-
tures [1–3]. The melting temperature of a DES can be as
technology, a discussion on the history of their synthesis
low as 12°C, indicating that it is in the liquid phase even at
in DESs and a future perspective on the use of DESs in this
room temperature [2]. DESs are often mistakenly consid-
area are needed.
ered to constitute a subtype of ionic liquids (ILs) owing to
their similar physical properties. Their chemical proper-
ties, however, are significantly different from those of ILs
because the starting mixtures of DESs typically include a 2 H
 ow do DESs control the
halide salt and a hydrogen bond donor (HBD), in contrast
to a simple cation and anion pair for ILs [4]. Since the first
­structures of gold nanomaterials?
report of DESs in 2001 [1], they have been highlighted as
In 2008, Sun et  al. reported the synthesis of gold nan-
environmentally benign media with advantageous char-
oparticles with various unique shapes such as stars,
acteristics and have been investigated mainly in metal
snowflakes, and thorns using a DES composed of choline
processing applications, such as metal electrodeposition
chloride and urea with a mole ratio of 1 : 2 (Figure 2) [18].
and electropolishing. In particular, DESs are highly attrac-
In spite of the unusually lengthy synthetic procedure
tive for large-scale industrial electroplating processes
(1 week), the presence of high-index facets enabled the
*Corresponding author: Jae-Seung Lee, Department of Materials nanoparticles to be used in the electrocatalytic reduction
Science and Engineering, Korea University, 145 Anam-ro, Seongbuk- of H2O2. This pioneering work demonstrated three impor-
gu, Seoul 02841, Republic of Korea, e-mail: JSLEE79@korea.ac.kr tant points that require consideration in the chemical
272      J.-S. Lee: Deep eutectic solvents as versatile media

Figure 1: Chemical structures of halide salts and hydrogen bond donors (HBDs).
Reprinted with permission from Ref. [4]. Copyright 2014 American Chemical Society.

Figure 2: Various shapes (snowflakes, stars, and thorns) of gold nanoparticles synthesized in a DES.
Reprinted with permission from Ref. [18]. Copyright 2008 WILEY-VCH Verlag GmbH & Co.

design of DES-based synthesis of noble metal nanoma-
terials: (1) the DES exhibited dual functions as a reac-
tion medium and a shape-directing agent (SDA); (2) the
dry synthesis (free of H2O) using the DES required sig-
nificantly longer reaction time compared to the reaction
under aqueous conditions; and (3) the size of the nano-
particles was not (able to be) controlled. The discovery
that DESs can act as an SDA could lead to advancement
in the synthetic strategies for nanomaterials. Further-
more, the vast chemical library of HBDs as a potential
component of DESs could be useful for exploring the
chemical interactions of specific functional groups at the
interface of a DES and nanoparticle.
Research into the role of DESs in nanoparticle synthe-
sis is still in its infancy, and therefore, there is still a long
way to go to fully understand their chemical functions. For
example, the shape-controlled synthesis of silver nano­
materials by polyvinylpyrrolidone is still under active inves-
tigation since the first report of this synthesis 15  years ago
[19]. The kinetically unfavorable synthetic reaction in a DES
emphasizes the importance of conventional solvents, par-
ticularly H2O, to facilitate fast reactions. The reduction of a

gold precursor (typically AuCl4−) by ascorbic acid inevitably
involves deprotonation of ascorbic acid [20] and, thus, is
significantly enhanced in a protonatable solvent. Although
most of the HBDs have protonatable chemical groups such as
hydroxyl or carboxyl groups, they would not be expected to
participate in the deprotonation of ascorbic acid because of
their mutual hydrogen-bonding interactions to form the DES,
leading to the deactivation of ascorbic acid. This specula-
tion is conversely supported by the accelerated reaction rate
(reaction time of a few hours) achieved by the addition of
trace amounts of H2O (e.g. at a concentration of 5000 ppm).
In fact, most studies report a reaction time of just several
hours even without the intentional addition of water, which
is likely because of the hygroscopic nature of the DESs [21,
22]. There is still room to systematically control the size of
noble metal nanoparticles during their synthesis in DESs by
separating the nucleation and growth stages. Adaptation of
the seed-mediated growth method to the DES media would
be a reliable and reasonable starting point.
Three potential routes of structural control of DESs
on the shape of nanoparticles can be predicted. First, the
halide ions in DESs, depending on the type and concen-
tration, may exhibit the shape-directing properties as they
do in aqueous phases for various anisotropic gold nano-
structures [23, 24]. Although the exact role of halide ions in
the aqueous synthesis of gold nanoparticles still remains
the subject of much debate, their effect on the surface
of gold nanoparticles during the growth in DESs would
be another interesting issue to investigate. Second, the
facet-specific preferential adsorption of hydrogen bond
donors (HBDs) on gold nanoparticles during the growth
is expected to result in their anisotropic shapes. In fact, a
number of HBD molecules contain amine, hydroxyl, and
carboxyl groups in either aliphatic or aromatic molecular
frames (Figure 1), which is structurally similar to previ-
ously investigated shape-directing agents (SDAs) used in
aqueous media for gold nanoparticles [25, 26]. Finally, the
addition of conventional SDAs such as polyvinylpyrro-
lidone (PVP) or bis(p-sulfonatophenyl)-phenylphosphine
(BSPP), depending on their solubility in DESs, may result
in the controlled shape of the gold nanoparticles [27, 28].
3 DESs with water
The presence of water in DESs during the synthesis of noble
metal nanoparticles not only determines the reaction rate
but also the morphology of the nanoparticles such as their
size and shape. For example, our group has synthesized
gold microstructures with a large structural diversity with
J.-S. Lee: Deep eutectic solvents as versatile media      273
respect to their diameter and surface roughness by simply
varying the ratio of water and DES in the mixture [29].
There are several follow-up reports, which demonstrate
that the water content is one of the most important para­
meters for the precise morphological control of noble metal
nanostructures in DESs (Figure 3) [30–33]. In addition to
the water content, other factors such as temperature, ratio
of reductant to AuCl4−, additional SDAs, and electrochemi-
cal potential have been investigated as effective variables
to control the morphology of the nanostructures synthe-
sized in DESs [29, 34–36]. Despite the considerable effect
of water, however, the addition of water to DESs needs to
be more carefully reviewed because water, itself, is both
a hydrogen bond acceptor (HBA) and HBD. Water mole-
cules can interact with individual components of DESs by
forming multiple hydrogen bonds, leading to the breakage
of the halide salt-HBD interactions of DESs [22, 37]. This
breakage is the major difference between the use of DESs
and ILs. Therefore, it is difficult to determine whether a
mixture composed of, for example, water and Reline (a
common DES consisting of choline chloride and urea) at a
90 : 10 ratio is a true mixture of water and the DES or just
an aqueous solution of choline chloride and urea.
4 Current limitations of DESs
( 1) Incompatibility with silver: The halide anion of DESs
poses the greatest barrier to their application as media for
the synthesis of noble metal nanomaterials. Specifically,
the halide anion of DESs in the reaction mixture irrevers-
ibly forms solid silver halide with Ag + , which fundamen-
tally limits the application of DESs for the synthesis of silver
nanomaterials. This limitation explains why DESs have
been used mostly in gold nanomaterial synthesis to date.
There have been a few reports on the use of DESs in silver
nanomaterial synthesis, but they are limited to only films
and particles grown or supported on a solid substrate [38,
39]. To the best of my knowledge, every DES reported to
date contains a halide anion, indicating that it would take
a certain amount of time until this incompatibility issue in
silver nanomaterial synthesis is solved.
( 2) Thermal instability: DESs are known to exhibit suffi-
cient chemical stability to allow for their use in industrial
applications. At elevated temperatures with particular
combinations of HBDs and halide salts, however, their
thermal stability decreases as a function of reaction
time. For example, urea, one of the most frequently used
HBDs to form DESs, has been observed to decompose into
274      J.-S. Lee: Deep eutectic solvents as versatile media
Figure 3: Gold nanostructures having various structures synthesized in DESs with water content of 10% (A), 20% (B), 50% (C), 80% (D),
90% (E) and 100% (F).
Reprinted with permission from Ref. [31]. Copyright 2016 Royal Society of Chemistry.
ammonia at 80°C for an elongated reaction time period
in the presence of choline chloride, the most frequently
used halide salt, or other polyols [37, 40]. It is important to
note that pure urea is highly stable and does not decom-
pose under the same conditions. Its participation in the
formation of DESs leads to destabilization and thermal
decomposition when heated. In our group, we also have
observed that the color of DESs turns brown and brown-
ish black after heating for hours during nanomaterial syn-
thesis (data not shown). In fact, the extremely low vapor
pressure of DESs prevents them from boiling and releas-
ing heat. Therefore, unlike other conventional solvents,
DESs will thermally decompose when overheated. This
thermal instability of DESs can be an issue when noble
metal nanomaterials are synthesized at a high tempera-
ture over a lengthy reaction time (which is typical when
water is not used) because the decomposition of urea will
change the reaction conditions significantly. For example,
the generation of NH3 will dramatically increase the pH
of the reaction mixture, which can dramatically affect the
nucleation and growth of the noble metal nanomaterials
[41, 42]. The decomposition of one of the components of a
DES will eventually lead to the phase change of the DES,
after which the DES may no longer be a solvent.
(3) High viscosity: Synthetic researchers in nanosci-
ence are always in pursuit of high monodispersity of
noble metal nanomaterials. To achieve this goal, the
homogeneity of the reaction mixture is often ensured by
physical methods such as stirring, vortexing, or rotating.
More importantly, however, there is a chemical condi-
tion that precedes the physical methods: low viscosity of
the solvent. For complete homogenization and dissolu-
tion of noble metal precursors, reductants, and SDAs in
a DES, the viscosity of the DES must be as low as pos-
sible. Unfortunately, however, the viscosity of DESs is,
in general, several 100 times as high as that of water at
room temperature [4]. This high viscosity could be one
of the reasons why only a few DESs have been demon-
strated for the synthesis of noble metal nanoparticles to
date, despite the huge chemical library of halide salts and
HBDs. The viscosity of DESs can be reduced at elevated
temperatures. However, this is countered by the DESs
becoming thermally unstable.
(4) Overcoming the limitations: There could be poten-
tial solutions to overcome the aforementioned limitations
of DESs. For example, monovalent anions such as NO3− or
CH3COO− could be substituted for halide ions to make DESs
comparable with silver. The thermal stability of DESs could
be enhanced using component molecules having stronger
atomic bonds such as double or triple bonds. However, it
is still a question if non-halide salts can form DESs with
conventional hydrogen bond donors (HBDs). Moreover,
molecules having double or triple bonds could be thermally
polymerized at a higher temperature that is required for the
formation of DESs [43]. In fact, because the chemical nature
of DESs, itself, causes their intrinsic problems discussed

Figure 4: (A) Palladium and (B) platinum nanostructures synthesized in a DES.
Reprinted with permission from Refs. [46] and [47]. Copyright 2012 and 2013 American Chemical Society.
above, it would be highly difficult to overcome the limita-
tions in the near future.
5 F uture of DESs for Nobel
­nanomaterial synthesis
In addition to the aforementioned advantages and disad-
vantages, there are a few more attractive points associated
with the use of DESs as the reaction medium for noble
metal nanomaterial synthesis, which are as follows:
( 1) Excellent solvent: The high solubility of various
types of materials such as metal salts, metal oxides, solid
halogens, small organic molecules, polymers, and even
gaseous molecules in DESs substantially enlarges their
pool of potential reactants [4, 44]. By conducting noble
metal nanomaterial synthesis using noble metal precur-
sors and other metallic and non-metallic starting materi-
als, all dissolved together in a DES, one can expect that
highly functional nanomaterials could be synthesized
Number of publications
with improved chemical stability, increased catalytic
properties, and more distinctive optical properties.
( 2) Green media for nanofabrication using polymers:
After synthesis, noble metal nanomaterials are often
coated with polymeric materials to enhance their stabil-
ity by protecting their surface and to introduce chemical
groups for surface functionalization. In fact, DESs are
efficient “green” solvents for both radical and conden-
sation polymerization reactions, in general [45]. To the
best of my knowledge, however, post-synthesis fabrica-
tion of noble metal nanomaterials using polymers in a
DES has been rarely investigated to date. Synthesis and
J.-S. Lee: Deep eutectic solvents as versatile media      275
surface coating of noble metal nanomaterials by subse-
quent polymerization in a DES, preferably in a one-step
process, would be one of the next goals to achieve in this
area of research.
(3) Synthesis of platinum and palladium nanoma-
terials: In addition to gold and silver nanomaterials, a
few other noble metal nanomaterials such as those made
from platinum and palladium have been synthesized in a
DES (Figure 4) [46–50]. In contrast to the well-developed
aqueous synthesis of platinum and palladium nanoparti-
cles, there are only a few reports demonstrating the syn-
thesis of these nanoparticles in a DES. The platinum and
palladium salts were reduced by electrochemical reactions,
which resulted in only deposited, not dispersed, nano-
particles on a solid support, likely because of the limited
reducing power of chemical reductants in the DES. Con-
sidering the structural control of nanoparticles, including
60
50
40
30
20
10
0
2008 2009 2010 2011 2012 2013 2014 2015 2016
Year
Figure 5: Number of publications concerning the application of
DESs in nanotechnology as a function of year from 2008 to 2016.
Reprinted with permission from Ref. [16]. Copyright 2015 Elsevier B.
V. The data points of 2015 and 2016 were additionally obtained by
the author.
276      J.-S. Lee: Deep eutectic solvents as versatile media

Table 1: A summary of noble metal nanostructures synthesized in DESs to date and their properties and applications.

Element   Shapes   Size (nm)   Properties and applications   Reference number

Au   Concave rhombic dodecahedron, concave cube,    ~ 300   Electrochemical catalysis   [35]

octopod, cuboctahedral box, hollow octahedron
Au   Flower   30–500   SPR, SERS substrate   [32]
Au   Flower   200–1000   Catalysis   [30]
Au   Quasi-sphere   100–3000   Catalysis, surface   [29]
modification
Au   Star, dentist, quasi-sphere   200–2000   Electrochemical catalysis   [31]
Au   Foam   100–200 (pore)   Catalysis   [33]
Au   Quasi-sphere   25   X-ray contrast agent   [51]
Au   Star   300–900   Electrochemical catalysis   [34]
Au   Sheet   500–3000   Electrochemical catalysis   [36]
Au, Ag, Pd   Mesoporous film    ~ 30 (grain diameter)   SERS   [50]
Ag   Quasi-sphere    > 100 or  < 5   N/A   [38]
Ag   Porous film   20–40 (grain diameter)   Wettability   [39]
Pd   Quasi-sphere   10–20   N/A   [46]
Pt   Triambic icosahedron   158   Electrochemical catalysis   [48]
Pt   Flower   200   Electrochemical catalysis   [49]
Pt   Concave tetrahexahedron   62–370   Electrochemical catalysis   [47]

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preliminary stage and requires further investigation.
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6 Conclusions
The reaction medium in a solution-phase chemical reac-
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review the types, sizes, properties, and applications of
the noble metal nanomaterials, which are synthesized in
DESs to date, a summary is provided in Table 1.
Acknowledgment: This work was supported by the
National Research Foundation of Korea, funded by the
Korean government (NRF-2015R1C1A1A01053865, NRF-
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