nanomaterials

Review
Design Strategy and Application of Deep Eutectic Solvents for
Green Synthesis of Nanomaterials
Nguyen Nhat Nam 1 , Hoang Dang Khoa Do 2 , Kieu The Loan Trinh 3, * and Nae Yoon Lee 3, *

1 Biotechnology Center, School of Agriculture and Aquaculture, Tra Vinh University,

Tra Vinh City 87000, Vietnam
2 NTT Hi-Tech Institute, Nguyen Tat Thanh University, Ward 13, District 04, Ho Chi Minh City 700000, Vietnam
3 Department of BioNano Technology, Gachon University, 1342 Seongnam-Daero, Sujeong-Gu,
Seongnam-Si 13120, Republic of Korea
* Correspondence: [email protected] (K.T.L.T.); [email protected] (N.Y.L.)

Abstract: The first report of deep eutectic solvents (DESs) was released in 2003 and was identified as
a new member of ionic liquid (IL), involving innovative chemical and physical characteristics. Using
green solvent technology concerning economical, practical, and environmental aspects, DESs open
the window for sustainable development of nanomaterial fabrication. The DESs assist in different
fabrication processes and design nanostructures with specific morphology and properties by tunable
reaction conditions. Using DESs in synthesis reactions can reduce the required high temperature and
pressure conditions for decreasing energy consumption and the risk of environmental contamination.
This review paper provides the recent applications and advances in the design strategy of DESs for
the green synthesis of nanomaterials. The strategy and application of DESs in wet-chemical processes,
nanosize reticular material fabrication, electrodeposition/electrochemical synthesis of nanostruc-
tures, electroless deposition, DESs based nano-catalytic and nanofluidic systems are discussed and
highlighted in this review.

Keywords: deep eutectic solvent; nanostructure fabrication; nanofluid; green solvent; electrodeposition

Citation: Nam, N.N.; Do, H.D.K.;

Trinh, K.T.L.; Lee, N.Y. Design
1. Introduction
Strategy and Application of Deep
Eutectic Solvents for Green Synthesis The distinct properties of solvents contribute significantly to research outcomes and
of Nanomaterials. Nanomaterials 2023, processes in various industrial areas [1–3]. Solvents assist in making optimal media for
13, 1164. https://doi.org/10.3390/ chemical reactions and participate in the different chemical processes. However, releasing
nano13071164 solvents after being used has caused harm to the environment and human health [4,5].
Therefore, different methods have been developed to evaluate the risk of solvent to the
Academic Editors: Shaolong Wu,
Long Wen and Xiaobo Hu
environment [6–9]. For example, the conductor-like screening model for realistic solvation
(COSMO-RS) quantum chemical computation has been employed to screen chemical reac-
Received: 13 February 2023 tion solvents [10]. Additionally, the industrial processes based on solvents were evaluated
Revised: 12 March 2023 by the environmental index (IEI) [9]. The harmful outcomes of solvent waste resulted in
Accepted: 16 March 2023 utilizing new environment-friendly and biodegradable solvents. Using solvents in organic
Published: 24 March 2023
chemistry revealed using different solvents for organic synthesis [11]. Nature has different
solvents that can be used for chemical reactions and processes [12]. The ingredients for
making bio-solvents included animal fat, fruit peels, sugarcane, corn, and wood, which
Copyright: © 2023 by the authors.
produce ion liquids, alkanes, aromatics phenolics, esters, furans, and ethers [13]. These
Licensee MDPI, Basel, Switzerland. bio-solvents exhibit properties similar to petroleum-based solvents but are biodegradable
This article is an open access article and recyclable. Consequently, there was a trend of screening for green solvents to reduce
distributed under the terms and the environmental damage caused by hazardous solvents [14]. Due to their unique advan-
conditions of the Creative Commons tages and characteristics, such as biodegradability and recyclable nature, green solvents are
Attribution (CC BY) license (https:// widely used in several industries, including pharmacy and food processing [15,16]. The
creativecommons.org/licenses/by/ discovery of new green solvents has revealed new candidates for different substrates. For
4.0/). example, triazolium-based ionic liquids have been proposed for breaking up the molecular

Nanomaterials 2023, 13, 1164. https://doi.org/10.3390/nano13071164 https://www.mdpi.com/journal/nanomaterials

Nanomaterials 2023, 13, x FOR PEER REVIEW 2 of 31

nature, green solvents are widely used in several industries, including pharmacy and
Nanomaterials 2023, 13, 1164 food processing [15,16]. The discovery of new green solvents has revealed new candi- 2 of 29
dates for different substrates. For example, triazolium-based ionic liquids have been
proposed for breaking up the molecular connection of cellulose and can assist with using
cellulose-originated
connection of celluloseingredients
and can [17].assistAwith
notable
usingfinding was DESs, which
cellulose-originated were first[17].
ingredients an-
Anounced
notableby Abbott
finding waset al. in 2003
DESs, which[18].were
DESs, a famous
first announcedIL, exhibited
by Abbott features
et al. inof 2003
phase[18].
be-
haviors
DESs, and physical
a famous properties
IL, exhibited in other
features ILs [19,20].
of phase Generally,
behaviors DESs, which
and physical are prepared
properties in other
by [19,20].
ILs combining two or
Generally, three
DESs, biodegradable
which are prepared components
by combining of two
hydrogen
or threebond acceptors
biodegradable
(HBAs) andofhydrogen
components hydrogenbond bonddonors
acceptors (HBDs),
(HBAs) can
andbehydrogen
considered bondgreen solvents
donors (HBDs),[21,22].
can
Because
be of thegreen
considered characteristics of versatility,
solvents [21,22]. Because nontoxicity, and biodegradability,
of the characteristics DESs have
of versatility, nontoxicity,
and
beenbiodegradability,
utilized in different DESs have[23].
fields been In utilized in different
the biological fields have
field, DESs [23]. been
In the biological
used to ana-
field, DESs havematrices
lyze biological been used to analyze
regarding biological
clinical matrices regarding
and toxicological clinical
objects [24]. DESsand toxico-
effectively
logical
extract objects [24]. DESs
biomolecules (i.e., effectively extract biomolecules
proteins, carbohydrates, (i.e., [25].
and lipids) proteins, carbohydrates,
Previously, reviews
and lipids)provided
on DESs [25]. Previously,
essential reviews on DESs
information andprovided
generalessential information
applications [26,27]. and
DESs general
effec-
applications
tively produced [26,27]. DESs
novel andeffectively produced(i.e.,
refined materials novel and refined
plasmonic materials
metal (i.e., plasmonic
nanoparticles) [28,29].
metal
In thisnanoparticles) [28,29]. of
review, applications In DESs
this review, applications
for nanomaterial of DESs for
fabrication nanomaterial
were summarized, fabri-
in-
cation were summarized, including the areas of solvent media, reticular
cluding the areas of solvent media, reticular nanomaterials, electrodeposition, electroless nanomaterials,
electrodeposition, electroless deposition,
deposition, functionalization, functionalization,
nano-catalytic nano-catalytic
and nanofluidic systems and nanofluidic
(Figure 1). This
systems
specific (Figure 1). This specific
review provides review
the current provides
status of thethe current status
applications of the
of DESs in applications
the design and of
DESs in the of
fabrication design and fabrication of nanomaterials.
nanomaterials.

Figure1.1.The
Figure Theapplications
applicationsof
ofdeep
deepeutectic
eutecticsolvents
solvents(DESs)
(DESs)for
fornanomaterial
nanomaterialfabrications.
fabrications.

2.2. Fundamental
Fundamentalof ofDES
DES
The
The combinationofofHBAs
combination HBAsand and HBDs
HBDs results in in
results thethe
formation
formationof aoftype of green
a type solvent
of green sol-
called deep eutectic solvent or DES [30]. The number of HBA
vent called deep eutectic solvent or DES [30]. The number of HBA and HBD can and HBD can be altered
be al-
with
teredrespect to the different
with respect classes ofclasses
to the different DESs. Typically, an approximate
of DESs. Typically, ratio of quaternary
an approximate ratio of
ammonium salts with metal salts is used to make DESs.
quaternary ammonium salts with metal salts is used to make DESs.
Five
Five types
typesof ofDESs
DESshave
havebeen
beencharacterized
characterized based
based ononthe
thecomponents
components of of HBAs
HBAs andand
HBDs. In I, II, III, and IV types, HBAs contain a halide anion and a quaternary
HBDs. In I, II, III, and IV types, HBAs contain a halide anion and a quaternary ammo- ammonium
cation
nium (mainly cholinecholine
cation (mainly chloridechloride
was used).
wasHowever, HBDs areHBDs
used). However, different among the
are different different
among the
types. For example, type I DESs have metal chloride as HBD, whereas
different types. For example, type I DESs have metal chloride as HBD, whereas hydrated hydrated metal
chloride and organic molecules are present in types II and III. In type IV, metal halides and
metal chloride and organic molecules are present in types II and III. In type IV, metal
urea act as HBDs. The recently developed type V comprises natural resources for HBAs
halides and urea act as HBDs. The recently developed type V comprises natural resources
and HBDs, such as acetic acid, caffeine, DL-Menthol, lauric acid, pyruvic acid, tetracycline,
for HBAs and HBDs, such as acetic acid, caffeine, DL-Menthol, lauric acid, pyruvic acid,
and tryptophan [31]. The hydrophilic DESs have been classified into types I and II. In
tetracycline, and tryptophan [31]. The hydrophilic DESs have been classified into types I
contrast, hydrophobic DESs were categorized into types III and IV [32]. A new class of
and II. In contrast, hydrophobic DESs were categorized into types III and IV [32]. A new
DESs has been described as non-ionic solvents of which hydrogen bonding is especially
class of DESs has been described as non-ionic solvents of which hydrogen bonding is
predominant [21]. This new type V has a general formula as RZ + RP, where Z = CONH2 ,
especially predominant [21]. This new type V has a general formula as RZ + RP, where Z
COOH, OH and P = C6 H4 OH, CO, NH2 . DESs generally have highly tunable chemical
and physical properties. The properties of DESs typically depend on the nature of the
HBA/HBD combination, molar ratio, water content, and temperature [27].
The wide applications of DESs in nanotechnology fabrication can be considered by
their relatively high conductivity, low volatility, and high thermal stability. The properties
Nanomaterials 2023, 13, 1164 3 of 29

of DESs could be actively driven to use them as a green solvent in chemical processes. The
structure of HBDs and hydrogen bonding proton transfer mechanism has been reported
to determine the properties of DESs. Different HBDs, including urea, polyhydric acid,
polyhydric alcohols, and saccharides, have been explored [33]. Hydrogen bond interactions
activated the carbonyl and guanidine groups. Some HBDs of 1,2-propanediol and urea
established a strong intermolecular account for the extraction efficiency. The designable
mixtures of HBAs and HBDs resulted in different features of DESs [34]. A new liquid phase
can be produced from hydrogen bonding based on a eutectic mixture and self-associate
originating from HBAs and HBDs. The capability of providing electrons and protons of
compounds that have high affinity to DESs enabled various dissolution properties [20].
Another attractive aspect of DESs is the capability of producing various eutectic mixtures
that include two non-faceted phases. These mixtures trigger the formation of regular
particles that exhibit continuous edgewise growth in melts [32]. Additionally, the melting
point of eutectic mixtures is lower than its components due to the effect of hydrogen
bonding on the self-assembling capacity of DESs.
The hydrophilicity and hydrophobicity properties of DESs can be considered. The
hydrophilic and hydrophobic DESs have been compared for sulfonamide pretreat deter-
mination [35]. This study prepared and identified seven types of HBDs, and only three
hydrophilic ones could form an aqueous two-phase system for targeted extraction. Among
the HBDs, ChCl-Ph exhibited the lowest cooling point (−68.9 ◦ C) and viscosity (0.014 Pa·s).
Moreover, there was a higher density of hydrophilic DESs than water. For example, the
densities of ZnCl2 -Urea (1:3.5) and ZnCl2 -acetamide (1:4) were 1.63 and 1.36 g cm−3 , re-
spectively [36]. Based on specific requirements, different combinations of components
can be used to modify the properties of hydrophobic DESs (i.e., vapor pressure, thermal
stability, liquid range, and incombustibility) [37]. The first hydrophobic DES was identified
while designing water-immiscible solvents as hydrophilic DES [38]. In this work, the
HDES consists of decanoic acid, which is highly hydrophobic and a quaternary ammonium
salt. The alkyl chain affects the equilibrium and hydrophobicity of the DES-water system.
The improvement of volatile fatty acids from diluted aqueous solutions was successfully
observed by using as-synthesized DESs. Different from hydrophilic DESs, the density of
hydrophobic counterparts ranged from 0.88–0.97 g cm−3 . The hydrophobic DESs exhibited
contact angles ranging from 47.9–78◦ and were less polar than the hydrophilic counterparts.
DESs are analogous to ILs regarding physicochemical properties, including density,
electrical conductivity, miscibility, viscosity, and freezing point [39,40]. The strength of
intermolecular interactions among DESs components governs viscosity, one of the most
critical parameters of DESs [41]. Typically, the more polar the solvent, the more viscous
it is compared to non-polar solvents. Most of the DESs exhibit relatively highly varying
viscosities. It was observed that DESs with bromide anions are more viscous than chloride
anions and lower viscosities DESs only contain long-chain fatty acids. The viscosity model
of DESs obtained from the group contribution method has been recently reported [42]. The
model predicted high accuracy of DESs viscosity using input parameters of temperature
and composition and could be a powerful tool for discovering the viscosity of DESs.
Regarding nanomaterial fabrication, the viscosity and surface tension of DESs is key
physicochemical features that have a high impact on the interface and colloids [43]. The
surface tension and viscosity are related to the cohesive forces and interactions between
components of the surface [44]. Less viscosity of DESs can increase the ion species mobility
and interaction forces between ions improving the formation efficiency and the nucleation
of the nanostructure. Typically, the surface tension of DESs is impacted by HBD, HBA,
temperature, and water content. The molar ratio of HBA and HBD of DES determines
its surface tension. The high ratio increases the surface tension of DESs, investigating the
effect dominating the size-dependent mechanical properties of the nanostructures [45].
The mobility of ions in DESs correlated with the fluid viscosity and conductivity,
which hole theory can explain. It is assumed that there are holes in the liquid or molten
Nanomaterials 2023, 13, 1164 4 of 29

state. These holes are random in size and location and undergo constant flux. The size of
holes, radii of the average size void (r), is determined by the following equation [19]:
  3.5 k T
4π r2 = (1)
γ

where k is the Boltzmann constant, T is the absolute temperature, and γ is the surface
tension. Typically, the viscosity depends on the size of the voids, the size of migrating
species, and the radii of cations and complexed anions. Under low temperatures, the ions
transport into the vacant is reduced due to the smaller size of the holes and bigger size of
the ions. It is vice versa under high-temperature conditions. The hole theory can be used to
model and predict the viscosity and conductivity of DESs [46]. Most DESs are biodegradable
and friendly to the environment and ecosystem [47]. Since their emergence, DESs have
become a promising candidate for nanomaterial fabrication because of their economics,
sustainability, dissolution ability, biocompatibility, and outstanding designability [48].
The class of natural DESs has numerous attractions as novel organic solvents. The
properties of natural DESs are influenced by several factors, such as water content, tem-
perature, and component ratio [49]. For instance, in the natural DESs containing ChCl
(HBA), the viscosity in acid-based was observed to be higher than that of alcohol-based
natural DESs. The alcohol-based natural DESs of glycerol and 1,2-propanediol have rela-
tively lower viscosity. The citric acid-based natural DESs have high viscosity due to their
large molecular weight due to the three carboxyl groups that could interact with HBA.
The natural DESs with low molecular weight have a lower density than those with high
molecular weight. It is noticed that water addition decreased DESs’ density. The possible
mechanism is that the water molecules in natural DESs changed their molecular packing,
decreasing density [50].

3. Design Strategy and Application of DES for Nanomaterial Fabrication

Since the first reported use of DESs in the green synthesis of pentacle gold nanos-
tructure, DESs have become increasingly popular in the design strategy and fabrication
of nanostructures. DESs could be an effective medium for wet-chemical processes, elec-
trodeposition/electrochemical synthesis, and electroless deposition. DESs are involved
in the process and development of nanomaterial functionalization, nano-catalytic, and
nanofluid systems.

3.1. DES as a Solvent Medium for Wet-Chemical Approach

3.1.1. Preface
The bottom-up nanomaterial fabrication is based on the principle of nucleation and
growth of nanomaterials. In this approach, the atoms and molecules form nanoparticles or
complex nanostructures [51,52]. The process involves assembling ions or molecules into
nanoparticle formation in different theories and mechanisms [52]. Among the bottom-up
methods, the wet-chemical synthesis process includes precursors, surfactants, and solvent
media in the chemical reactions. Recently, the inexpensive constituents and easy prepa-
ration of DES allowed the large-scale synthesis of nanomaterials [53]. The DES-assisted
wet-chemical synthesis allowed obtaining nanosize with designable specific morphol-
ogy, shape, size, and properties by fine-tuning the reaction conditions [54,55]. Solvother-
mal/hydrothermal, template synthesis, self-assembly, and interface-mediated fabrication
are the typical wet-chemical synthesis routes for nanomaterials [56]. The bottom-up chem-
ical process involves a reaction of salts or organometallic precursors by decomposition,
thermolysis, or metathesis that determine the composition of final nanostructures [57].

3.1.2. Nanostructure Fabrication in DES as a Reaction Medium

DESs have been used for the fabrication of different nanostructures, including silver
nanoparticles [58–60], gold nanoparticles [61–63], magnetic nanoparticles [64–66], Zinc
nanoparticles [67], ZnSe nanoparticles [68], CZTS nanoparticles [69], upconversion nanopar-
Nanomaterials 2023, 13, 1164 5 of 29

ticles [70,71], as well as biopolymers, such as lignin nanoparticles [72,73] and cellulose
nanoparticles [74]. DESs can dissolve many different reagents and substances, including
high relative concentrations of metal salts, metal oxides, and various polymers. In green
chemistry, metallic nanoparticles can be biogenically synthesized using DESs to increase
the efficiency of reactions [75]. DES-based methods involve novel green solvents for nano-
material fabrication. The volatile and flammable media solvents are related to exposure
toxicity during process operation and hazard explosion. DESs can also reduce the potential
risk of pollution due to their negligible vapor pressure, which is safe and eco-friendly.
The employment of DESs during chemical reactions can reduce the application of high
temperature and pressure and decrease energy consumption for the fabrication process
and harmful impact on the environment. It is noticed that although green solvents can
synthesize nanostructures, some types of metal- and composite-based nanomaterials may
retain their risks of accumulation in organs or production of reactive oxygen species (ROS)
that directly or immediately affect human health [76]. ROS can cause biological disorders
such as lipid peroxidation, DNA damage, and protein denaturation.
DES-based methods involve novel green solvents for nanomaterial fabrication. DESs
control the size and shape of the nanoparticles. For instance, Dong and coworkers de-
scribed the dissolution of ZnO powders and precipitation of ZnO nanostructure in a choline
chloride and urea mixture [67]. A combination of facile green antisolvent and DES could on
the precipitation and dimension of the ZnO nanostructure. The injection time of dissolved
ZnO in DES (ZnO@DES) is a crucial factor in controlling the nanoparticle morphology.
Since choline chloride and urea are more soluble in water than antisolvent, ZnO can be
precipitated easily because of the significant driving force of water. The short injection time
of ZnO@DES makes a competitive development of particles in a less preferred direction.
Meanwhile, the provision of ZnO to support one-dimensional growth is limited in most
directions by slow injection time. Xiong and his coworker reported a one-step preparation
of hematite nano-spindles using DES containing choline chloride and urea [77]. In the
anhydrous reaction solution, Fe3+ would interact with NH3 produced from urea in the DES
medium to form Fe(NH3 )2 Cl3 . The reline has been used to control the morphology and
porosity of nanostructure ceria in the solvothermal method [78]. In the existence of reline,
the rate of the reaction was increased. The deep eutectic-solvothermal methodology using
green, economical, non-toxic solvents enabled the green synthesis of nanostructured ceria at
low temperatures, resulting in the development of large-scale manufacturing. Solvothermal
synthesis occurs in media solvents at wide and high ranges of temperatures and pressure
producing chemical compounds from reactants [79]. DESs can be employed in various
reactant systems in solvothermal methods to prepare various nanostructures. DESs can
dissolve different precursors and are followed by a solvothermal process under the desired
conditions. The deep eutectic-solvothermal allows for synthesizing and controlling nanos-
tructures with less energy consumption [78]. Likewise, DESs are latent supramolecular
catalysts that increase the reaction rate with solvent-driven pre-organization of the reactant
as a primary mechanism of deep eutectic-solvothermal methodology. Aqueous DES was
used for synthesizing magnetite (Fe3 O4 ) nanoparticles [64]. A wet-chemical reaction was
started from ferrous (II) sulfate with potassium nitrate in DES and water mixture. The mor-
phology of nanoparticles was affected by DES concentration and the different volume ratios
of water and DES. The advantages of DESs in nanosynthesis have been proven compared
to the less conventional ones. Adhikari and coworkers described preparing organosolu-
ble silver nanoparticles (AgNPs) using the free-halide DES-based wet-chemical reduction
method (Figure 2a) [59]. In this work, unconventional DESs systems (i.e., choline nitrate
and glycerol, choline chloride and glycerol, and choline acetate and glycerol) have been
designed. The innate incompatibility of halide-based DESs was solved by nitrate-based
DESs, resulting in a dispersed colloidal solution of AgNPs.
 by evaporating a mixture of zin chloride with HBDs (glucose and fructose) and amino
acids. T-DESs work as a reaction medium to obtain AgNPs by chemical reduction
Nanomaterials 2023,method.
13, 1164 The presence of urea may influence the chemical reaction by enhancing the 6 of 29

oriented attached mechanism [89,90].

Figure 2. (a) Schematic illustration

Figure 2. of the
(a) Schematic use of deep
illustration eutectic
of the solvents
use of deep (DESs)
eutectic in fabricating
solvents (DESs) in orga-
fabricating organosol-
nosoluble silveruble
nanoparticles. TEM image displays the well-dispersion and high
silver nanoparticles. TEM image displays the well-dispersion and high stability of of as-prepared
stability
as-prepared AgNPs synthesized in DES1 (choline nitrate and glycerol) after 40 days. Reprinted
AgNPs synthesized in DES1 (choline nitrate and glycerol) after 40 days. Reprinted with permission
with permission from ref. [59]. Copyright 2018 American Chemical Society. (b) Design of DES as a
from ref. [59]. Copyright 2018 American Chemical Society. (b) Design of DES as a green solvent for
green solvent for precipitating lignin nanoparticles with controllable size. Reprinted from ref. [72].
precipitating lignin nanoparticles with controllable size. Reprinted from ref. [72].
DESs have the capacity dissolution of different biopolymers, including cellulose,
The presence of DES in nanostructure fabrication has demonstrated a role in aggrega-
lignin, starch, and chitin. Recently,
tion controlling highly uniform
nanoparticle formationlignin
by NPs
SEMwere prepared
and TEM by a simple For instance,
characterization.
and environmental method (Figure 2b) [72]. Lignin is one of the most
DES made of choline chloride and citric acid has been used to synthesize abundant bi-highly uniform
opolymer that andhas monodispersed
limited solubility. Inoxide
iron this work, the DESsin(choline
nanoparticles chloride
nature [65]. and ethan- nanoparticles
The as-prepared
olamine/ethylene glycol /lactic acid) were used as “green solvents”
are not agglomerated. In this study, DES-capped magnetite enhanced with the ability to
the photodegradation
dissolve 20–40% industrial lignin and the formation of its nanoparticles. DESs and water
of organic pollutants and inhibited excellent anticancer behavior. Currently, DES composed
are miscible, and an interface
of choline membrane at(ChCl/Gly)
chloride/glycerol two-phase between
showed DESs andon
an effect water can be
the dispersion of carbon
formed by highly hydrophobic
nanotubes lignin
in water molecules
[80]. The aqueousin theDES
soluble lignin-DESs
system [72,93].
disaggregates In thisnanotubes into
carbon
case, DESs function
smallerasbundles
less hydrophobic surfactant
that assist in controllingdispersed in colloidal
CO2 absorption. suspensions.
Superior In of single-wall
dispersion
another study,carbon
the natural acidic DES comprising choline chloride and oxalic acid
nanotubes (SWNTs) in water was provided by the net negative charge surface ofdihy-
drate is used toas-prepared
obtain cellulose
DESs nanocrystals, of repulsion
via electrostatic which theof crystallinity
sonication. yields 43.6 ± 1.9%
The optimized dispersions were
[74]. The applications of hydrogen bond donors and acceptors
explored through the study of ChCl/Gly concentrations (% mass inin different ratios canSWNTs concen-
water),
prepare acid DESs that
trations hydrolyze
(mg/L), the amorphous
and sonication energyparts
(J/mL).of cellulose.
Moreover,Recently, Lai and
the interdisciplinary application
coworkers used of cellulose
DESs has nanocrystals
been proven in (CNCs) and DES 3Dofprintable
the self-assembly ionogels
surfactants. [94]. The involves the
The phenomenon
micelle formation of cationic surfactants in designed DESs. The DES-surfactant behaviors
provide potential application in the fields of material synthesis due to their impact on the
degree of ionization, interface, and thermodynamic parameters [81].
DESs play a role in nanoparticle stability and well dispersity. The reline containing
choline chloride, and urea enables the effective formation of highly crystalline and nano-
Nanomaterials 2023, 13, 1164 7 of 29

sized fluorapatite nanoparticles [82]. The ionic strength and 3D-bulky alignment of reline
can control the growth and electrostatic stabilization of as-synthesized fluorapatite nanopar-
ticles. Notably, the electrostatic stabilization was accelerated by the high ionic strength
of DESs, blocking or weakening inter-particle collisions. Meanwhile, the steric repulsion
coordination between particles’ surfaces resulted from the bulky geometry of DESs, which
decreased agglomeration, leading to enhanced mono-dispersion of particles [82–84].
In solvothermal methods, DESs act as solvents and catalysts [85]. Fast synthesis of
ceria nanoparticles (CeO2 NPs) has been successfully achieved using reline as a chemical
process solvent [86]. The mixture of choline chloride and urea (1:2 molar ratio) was
used to make reline. The reaction medium’s molecular structure boosted the cerium
oxycarbonate’s fast nucleation growth. The quick formation of CeO2 NPs was achieved
in reline without the addition of corrosive NaOH or a large amount of input energy. In
this study, a varying amount of water was added to DESs to control CeO2 morphology. In
this case, the mixture of DESs and water works as greener processing and reaction media
where the reaction rapidly occurs under reasonable conditions. It has been reported that
the suitable addition of water can modify and improve the physicochemical properties of
DESs, such as viscosity. However, a certain additional amount of water in DESs should be
carefully studied due to the alteration of DES’s structure even at low hydration levels [87].
Although the water molecules show high interaction with different DESs components
through hydrogen bonding, the properties of DESs can be maintained to reasonably large
water content [88]. This situation controls and enhances DES properties and features while
maintaining their functions [89,90]. In hydrothermal synthesis, the existence of urea in DES
also triggered the formation of Ce(OH)CO3 and Ce2 O(CO3 )2 , which produced CeO2 [91,92].
Four kinds of ternary DESs (T-DESs) have been reported as green solvent mediums for
fabricating silver nanoparticles [60]. These T-DESs were prepared by evaporating a mixture
of zin chloride with HBDs (glucose and fructose) and amino acids. T-DESs work as a
reaction medium to obtain AgNPs by chemical reduction method. The presence of urea
may influence the chemical reaction by enhancing the oriented attached mechanism [89,90].
DESs have the capacity dissolution of different biopolymers, including cellulose, lignin,
starch, and chitin. Recently, highly uniform lignin NPs were prepared by a simple and
environmental method (Figure 2b) [72]. Lignin is one of the most abundant biopolymer that
has limited solubility. In this work, the DESs (choline chloride and ethanolamine/ethylene
glycol /lactic acid) were used as “green solvents” with the ability to dissolve 20–40%
industrial lignin and the formation of its nanoparticles. DESs and water are miscible, and
an interface membrane at two-phase between DESs and water can be formed by highly
hydrophobic lignin molecules in the soluble lignin-DESs [72,93]. In this case, DESs function
as less hydrophobic surfactant dispersed in colloidal suspensions. In another study, the
natural acidic DES comprising choline chloride and oxalic acid dihydrate is used to obtain
cellulose nanocrystals, of which the crystallinity yields 43.6 ± 1.9% [74]. The applications
of hydrogen bond donors and acceptors in different ratios can prepare acid DESs that
hydrolyze the amorphous parts of cellulose. Recently, Lai and coworkers used cellulose
nanocrystals (CNCs) and DES 3D printable ionogels [94]. The protocol resulted in strong
physical and printable inks by reducing the concentration and inducing the desulfation of
CNC at high temperatures. The lifetime of ionotropic was also increased because of high
mechanical toughness and self-healing capability.

3.2. Nanosized Reticular Material Fabrication

Recently, unique structures and properties of reticular materials have attracted con-
siderable interest in catalysis, energy storage, and sensors [95,96]. The flexibility of com-
position, structure, and pores of metal-organic frameworks (MOFs) and covalent organic
frameworks (COFs) are typically associated with and determined by the fabrication method
and design strategy [97]. The presence of DESs in the fabrication of reticular nanomate-
rials can control the formation of MOFs in many ways. DESs could act as solvents and
structure-directing agents or template-delivery agents for the architecture of MOFs [98].
Nanomaterials 2023, 13, 1164 8 of 29

In some cases, DESs components could be involved in the structure formation, and their
decomposition products formed under ionothermal conditions.

3.2.1. MOF Fabrication

DESs can improve the chemistry of MOFs. The components (i.e., cations, anions, and
neutral ligands) of DES have involved the structure formulation of MOFs [99]. They are
involved in the self-assembly process exclusively or in combination with other components
to form new types of chemistry. Notably, structure-directing effects can be exerted by
neutral ligand molecules (i.e., urea). For instance, they can bind to metal sites, and removing
neutral ligands could form porosity and open metal structures. Zhang and coworkers
have described a series of MOFs synthesized using three DESs. For example, different
distinct framework topologies can be generated using the self-assembly of lanthanide ions,
1,4-benzene dicarboxylate, and components of DESs [99]. The reported mechanisms include
the integration of cations-anions/neutral ligands. The new role of DES in MOF fabrication
has also been presented in the framework of zinc(II)-boron(III)-imidazolate porous (ZBIF1)
with an unusually pentagonal structure [100]. Either action (choline) or neutral ligand
(m-urea) is integrated into ZBIF1. The Zn-Cl bonding in ZBIF1 is typically inaccessible in
conventional hydrothermal synthesis but can be achieved in DES. This can be considered
the first metal-imidazolate framework fabricated from DES.
In aluminophosphate synthesis, the presence of DESs allows controlling the miner-
alized concentrations to be retained and work as a template for delivering the reaction
mixture [101]. The choline chloride/urea DES (melting at 12 ◦ C) has been employed to
create a zeotype framework (SIZ-2) [102]. The template configuration and the charge bal-
ance of the framework were supported by ammonium resulting from decomposition with
urea of DES. The maintenance of Al-O-P alternation was observed. However, the chemical
formula indicated that SIZ-2 is an interrupted structure, which has the benefit of comprising
anionic frameworks. Recently, transition MOFs based on oxalate-sulfate anions in DES have
been described by Xiong and coworkers [103]. A mixture of chloride and oxalic acid with a
molar ratio of 3:7 was used as the reaction medium to make a series of iron oxalatosufate
networks. Oxalate and sulfate anions were employed in the structure as connecting ligands
which performed the role of DES to act as an organic linker in the construction.
A new porous and bioinspired structure of Zr-based MOF, called UiO-66-Urea, was
formed following a post-synthetic coating and hydrogen bonds between UiO-66-Urea and
choline chloride [104]. Various HDBs can determine the different MOF frameworks in
DES [105]. The assembly of metal ions and conjugating ligands is significantly affected by
HBDs. This work created seven new transition MOFs from three DES mixture compounds
of choline chloride and urea/e-urea/m-urea. HBDs have been proven to work in multiple
roles in formatting various nanostructures, such as urea and e-urea acting as reactants
by bonding to the metal ions. The generation of NH4 + and CH3 NH3 + cations through
the hydrolysis of urea and m-urea contributes to the construction of the frameworks and
connection between metal ions and ligands as the templates or charge-balancing agents.

3.2.2. COF Fabrication

The assembly of organic components is one of the major principles for fabricating
COFs [102]. The strong covalent bonds in 2D and 3D crystal porous materials assist
COFs formation [106]. DES contributes to the crystallinity of COFs. For example, DESs
have been used as green media to avoid high temperatures, hazardous organic solvents,
and long reaction times in fabricating crystalline 2D and 3D COFs [107]. This study
used three DES-based ChCl (ChCl/Glycerine, ChCl/Urea, and ChCl/Ethylene glycol)
to enhance the crystallinity at an optimized concentration. The DESs were designed to
control the structures and properties by changing HBD and HBA. The tetrabutylammonium
bromide and imidazole-based DESs were recently used to fabricate carboxyl-functionalized
COF (TpPa-COOH) for dye absorption [106]. The as-prepared TpPa-COOH had open
channels and exhibited good porosity and crystallinity under the low vapor pressure
 been used as green media to avoid high temperatures, hazardous organic solvents, and
long reaction times in fabricating crystalline 2D and 3D COFs [107]. This study used three
DES-based ChCl (ChCl/Glycerine, ChCl/Urea, and ChCl/Ethylene glycol) to enhance the
crystallinity at an optimized concentration. The DESs were designed to control the
structures and properties by changing HBD and HBA. The tetrabutylammonium bro-
Nanomaterials 2023, 13, 1164 mide and imidazole-based DESs were recently used to fabricate carboxyl-functionalized 9 of 29
COF (TpPa-COOH) for dye absorption [106]. The as-prepared TpPa-COOH had open
channels and exhibited good porosity and crystallinity under the low vapor pressure of
DESs. Recently, Gao and coworkers described COF-DES inferred from
of DESs. Recently, Gao and coworkers described COF-DES inferred from 1,3,5-tris(4-
1,3,5-tris(4-aminophenyl)benzene and 2,5-dihydroxyterephthalaldehyde (Figure 3) [108].
aminophenyl)benzene and 2,5-dihydroxyterephthalaldehyde (Figure 3) [108]. The DES has
The DES has been used as a reaction medium instead of organic solvents to adjust pores
been used as a reaction medium instead of organic solvents to adjust pores and specific
and specific regions with high crystallinity. The interferences of some compounds can be
regions with
prevented highCOF-DES
by the crystallinity. The interferences
combination, of some
which is used compounds
for the can be prevented
selective adsorption of by
the COF-DES
flavonoids. combination, which is used for the selective adsorption of flavonoids.

Figure
Figure3.3.(a)(a)
TheThe
design and and
design application of deepofeutectic
application solvents (DESs)
deep eutectic as a(DESs)
solvents reaction
assolvent for solvent
a reaction
fabricating high crystallinity COF-DES. (b) SEM image, (c) TEM image, and (d)
for fabricating high crystallinity COF-DES. (b) SEM image, (c) TEM image, and (d) PXRD PXRD pattern of pattern
as-prepared COF-DES. Reprinted with permission from ref. [108]. Copyright 2021 American
of as-prepared
Chemical Society.COF-DES. Reprinted with permission from ref. [108]. Copyright 2021 American
Chemical Society.

3.3. Electrodeposition/Electrochemical Synthesis

3.3.1. Principles and Characterization
Electrodeposition is a convenient, flexible, low-cost, and environmentally safe method
for fabricating 2D and 3D materials of nanostructure coating and films [109–112]. The elec-
trodeposition process can fabricate different nanostructures and thin film coating using a
simple experimental setup and operation. It can avoid using aggressive chemical-reducing
agents [110]. DESs have broad applications for electrodeposition and electrochemical
fabrication of polymers, metals, alloys, and semiconductors in electrochemistry. Elec-
trodeposition is a versatile method for fabricating nanomaterials to improve materials’
characteristics and decorative and functional properties [55]. It has been observed that the
electrodeposition process is challenging to achieve in an aqueous solution due to water
hydrolysis, which can cause a hydrogen evolution reaction and low electrodeposition
current efficiency [113]. The electrodeposition in aqueous solutions is a negative reduction
potential [114], while DES provides innovative potential and relatively high conductivity
for green and effective electrodeposition for nanostructure architecture [115]. The nanos-
tructure of materials can be characterized by morphology, chemical composition, and
electrochemical analysis. Other physical and chemical properties have been considered for
studying properties, such as magnetism, resistance, thickness, and corrosion. Typically,
the surface morphology and chemical composition of the nanostructures is observed by
scanning electron microscope (SEM), transition electron microscope (TEM), and atomic
force microscopy (AFM) [112,116,117]. The energy dispersive X-ray spectrum (EDS), X-ray
diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) are used to identify the
Nanomaterials 2023, 13, 1164 10 of 29

structure and composition of the materials [118–120]. The electrochemical behavior of

the material can be obtained and analyzed by several parameters (i.e., cyclic voltamme-
try, electrochemical impedance spectroscopy, chronopotentiometry, and potentiodynamic
polarization study) [118,121,122].

3.3.2. Electropolymerization
Electrochemical methods are used to design polymer structures by adjusting the
electrochemical parameters [123]. The generated polymer may be directly deposited on
an electrode surface in its doped or undoped state under DESs media conditions. Hosu
and coworkers described the electrodeposition of nanostructured phenazine polymer
poly(methylene blue) (PMB) from ethaline DES on glassy carbon electrodes [124] and on
carbon nanotubes [125]. The polymer was obtained in different DES media at different scan
rates (ranging from 50–500 mV/s) to find the optimized conditions for nanostructured PMB
film formation [124]. The DES and scan rate influenced the formation of spherical polymer
nanostructures. The nanostructures were not well-defined for the 50 mV/1 formation scan
rate, and the diameter ranged from 160–300 nm. For 150 mV/1, ordered nanostructures
were obtained with sizes ranging from 40–70 nm and granular films. For 500 mV/1, some
cauliflower growths were obtained, and spherical nanostructures’ diameter ranged from
50–160 nm. The scan rate was a crucial factor influencing the nanostructure polymer film’s
structure, morphology, and electrochemical properties.
Different choline-based DESs have been studied for the electrosynthesis of polymers,
such as polyaniline (PANI) [126]. Under ethaline DES conditions, highly crosslinked PANI
nanoribbons were developed with a dimension of 80 nm and pores of around 150 nm.
The structure of PANI-Gly was more nanoparticulate with a pore size of 100–250 nm. No
significant polymerization of aniline can be claimed for PANI-Rel after twenty-four scans.
The electropolymerization of PANI was studied on propeline DES containing a molar
ratio of 1:2 of choline chloride and 1,2-ethanediol [127]. It was hypothesized that DES
brings polymers with an electrochemical and optical performance at much lower economic
and environmental costs. The polymer films were obtained from highly branched and
crosslinked structures of PANI nanoribbons to show the correlation between DES and poly-
mer performance, altering the optical and electrical properties. The electropolymerization
of poly(3,4-ethylene dioxythiophene) (PEDOT) was obtained in DESs that contain a reline
of choline chloride–urea and an ethaline of choline chloride–ethylene glycol [127]. The
electrodeposition of PEDOT also was reported in DESs with perchloric acid [128]. PEDOT
fabricated in DES medium comprised of choline chloride, urea (reline), and HClO4 showed
the best performance for detecting ascorbic acid, dopamine, and uric acid.
Recently, the growth of PANI in oxaline DES inferred from cyclic voltammetry, and
electrochemical quartz crystal microbalance was reported [129]. The cycling of the voltage
(ranging from 0.1–1.2 V) and 0.25 M aniline in Oxaline-based DES were used to deposit
PANI. In DESs, the insertion of anions increases the oxidation of the mass of the polymer
film. Remarkably, the mass increased on a cathodic sweep.

3.3.3. Electrodeposition of Metal-Based Materials

DESs in the electrodeposition and electrochemical process can be applied for different
purposes, such as functional surfaces, to achieve required hardness, brightness, magnetism,
electrocatalysis, corrosion, and wear resistance [130,131]. The electrochemical coating
deposited on the surface could improve substrate materials’ solderability, lubricant prop-
erties, and electrical conductance [132]. Because of the passivation of the electrode, it is
challenging to fabricate many metals and their alloys from the aqueous solvents, but it is
easily electrodeposited in DES. Several metal nanostructures based on nickel, copper, zinc,
aluminum, and their alloys fabricated in DES have been reported [55,115].
The electrodeposition of various metals using DESs is an attractive topic due to their
cost-effectiveness, easy preparation, and biodegradability [133]. Table 1 shows the common
use of DESs containing choline chloride for electrodepositing nanostructures of metals and
Nanomaterials 2023, 13, 1164 11 of 29

alloys. For example, performing electrodeposition of Ni from DES is more effective than
from an aqueous solvent [134]. The electrodeposition of Ni in DESs generally does not
require a surfactant to obtain a nanocrystalline structure with low surface roughness. It has
been reported that DESs provided a deposit site of nickel to different crystal structures [115].
Elsharkawaya and coworkers have reported the electrodeposition of Ni nanoparticles from
DESs with a size of 20 nm and uniform needle flower structure (Figure 4a) [134]. The
deposition process in ethaline required an overpotential of −154 mV and 350 mV for the
hydrogen evolution and oxygen evolution reaction, respectively. In another study by Gu
and coworkers [135], the nanostructured Ni films were synthesized by electrodeposition
with adjusting constant, pulse, and reverse pulse voltage to create micro/nano binary
surface of nanosheets, aligned nanostrips, and hierarchical flowers. The structure and
chemical composition of the metal film’s surface exhibited superhydrophobicity sponta-
neously without modifications. The study found that the process temperature was essential
for the surface roughness and topography of the Ni films. Specifically, at 90 ◦ C, the Ni
nanosheet thickness and the size of Ni grains were 10–20 nm and 10–50 nm, respectively.
Nanomaterials 2023, 13, x FOR PEER REVIEW 12 of 31
The study revealed that less viscosity of DES could increase ion species mobility, enhancing
Ni’s deposition efficiency and nucleation.

Figure4.4.(a)(a)Scheme
Figure Scheme of of
thethe electrodeposition
electrodeposition of NiNPs
of NiNPs in ethaline.
in ethaline. XRD of
XRD pattern pattern of synthesized
synthesized
Ni/PGE
Ni/PGEininDES DES (ethaline) andand
(ethaline) in acetate bath. bath.
in acetate The inset
Thegraph
inset displays the XRD the
graph displays pattern
XRDofpattern
PGE. of PGE.
TEM images show the deposited NiNPs from DES. Reprinted from ref. [134]. (b) Scheme of the
TEM images show the deposited NiNPs from DES. Reprinted from ref. [134]. (b) Scheme of the
DES-assisted electrodeposition of nanostructure Ni films on Cu substrate. The inset images show
DES-assisted
the electrolytes electrodeposition of nanostructure
and SEM of as-fabricated nano-Ni films.Ni films onwith
Reprinted Cu permission
substrate. from
The inset images show
ref. [136].
the electrolytes
Copyright and SEM of as-fabricated nano-Ni films. Reprinted with permission from ref. [136].
2018 Elsevier.
Copyright 2018 Elsevier.
DESs demonstrate excellent properties of electrolyte and electrochemical behaviors.
DES can be a potential electrolyte that plays a critical role in metal and metal nanoparticle
electrodeposition. For instance, Ni and Sn nanoparticles were synthesized using a dif-
ferent type of DESs as a synthetic medium and the electrolyte of the electrochemical fab-
rication method [137]. Wang and coworkers have described the electrodeposition of
nano-Ni films using DES (Figure 4b) [136]. Similarly, Gu and coworkers have reported
Nanomaterials 2023, 13, x FOR PEER REVIEW 13 of 31

carbon substrate from DES of choline chloride and urea (Figure 5a) [140]. It was observed
Nanomaterials 2023, 13, 1164 that hydrogen bonds were formed between hydroxide groups and the DES 12 components.
of 29
Additionally, a dense distribution of Ni nanostructures could be observed.
The electrodeposition of 1D tellurium (Te) nanostructures on the gold surface have
beenDESs
described in DESs
demonstrate based properties
excellent on ChCl-U of and ChCl-EG
electrolyte [141]. The electrocrystallization
and electrochemical behaviors.
followed
DES can bea a3D-bulk
potentialcoagulation mechanism
electrolyte that withrole
plays a critical growth control
in metal by diffusion.
and metal nanoparticle The plat-
electrodeposition.
ing For instance,
solution of ChCl-EG and Ni and Snexhibited
ChCl-U nanoparticles were synthesized
a sweeping potentialusing a different
between 0.6–1.0 V of
type ofvoltammograms.
cyclic DESs as a syntheticThe medium and theand
Te nuclei electrolyte of the electrochemical
the nanostructure growthfabrication
were gradually
method [137]. Wang and coworkers have described the electrodeposition of nano-Ni
formed on the substrate in DES mediums (Figure 5b). The surface morphology of Te
films using DES (Figure 4b) [136]. Similarly, Gu and coworkers have reported developing
electrodeposited films was observed with a uniform distribution of hexagonal Te rods on
nanocrystalline Ni by electrodeposition in choline chloride and ethylene glycol [138]. Li
the
andAu surface.have
coworkers In other work,
reported Hammons and coworkers
the electro-codeposition of Ni-SiOhave described using DES for
2 nanocomposite coating
the
by DES-ChCl-EG to improve the corrosion resistance [139]. Co-deposition of[142].
electrodeposition of Pd nanoparticles into 2D superstructures Thethe
SiO2 into DES was
prepared by from
metal pattern recrystallizing
an aqueouscholine
solutionchloride and urea
is challenging. (ratiothe
However, ofstudy
2:1). revealed
Two temperatures
the
were used
stability for2 the
of SiO electrodeposition
nanoparticles in ChCl-EG process
without due to theirMoreover,
additives. influencetheonexistence
the viscosity
of and
SiO nanoparticles
conductivity
2 significantly affected the nucleation mechanisms of Ni. Consequently,
of the DES. The SEM characterized the nanoparticle morphology to show
the fabrication
large particlesofofmetal matrix
~20 nm nanocomposite
at 44.5 °C and smallcoatings can beof
particles processed
~10 nm effectively
at 32.5 °C.using
The role of
DES. The Ni nanostructure has been deposited on the carbon substrate from DES
DES was confirmed as a stability agent of the nanoparticles in the electrochemical pro- of choline
chloride and urea (Figure 5a) [140]. It was observed that hydrogen bonds were formed
cess. Similarly, direct and pulse current electrodeposition of Pd from a mixture of DES
between hydroxide groups and the DES components. Additionally, a dense distribution of
component and palladium
Ni nanostructures (II) chloride was reported [143].
could be observed.

5. (a)
Figure 5.
Figure (a)FE-SEM
FE-SEMimages
imagesof of
thethe
as-prepared nickel
as-prepared nanostructures
nickel by electrodeposition
nanostructures process process
by electrodeposition
from DES
from DES (ChCl-U)
(ChCl-U)ononglassy carbon
glassy (above)
carbon and and
(above) schematic of theof
schematic formation of hydrogen
the formation bonds bonds
of hydrogen
between hydroxides
between andand
hydroxides DESDES
components-based ChCl-U ChCl-U
components-based (below). Reprinted
(below). with permission
Reprinted withfrom
permission
from ref. [140]. Copyright 2017 American Chemical Society. (b) AFM images of Te electrodeposits
Nanomaterials 2023, 13, 1164 13 of 29

ref. [140]. Copyright 2017 American Chemical Society. (b) AFM images of Te electrodeposits
on Au-coated FTO electrode from DES of ChCl-EG at (i) 30 ◦ C (E = −0.04 V for 1.20 s) and
(ii) 80 ◦ C (E = 0.16 V for 0.50 s); and DES of ChCl- U DES at (iii) 30 ◦ C (E = −0.28 V for 0.80 s)
and (iv) 60 ◦ C (E = −0.22 V for 0.50 s). Histogram displays the diameter distribution of 1D Te nanos-
tructure obtained from ChCl-EG at (v) 30 ◦ C and (vi) 80 ◦ C; and from ChCl-U at (vii) 30 ◦ C and
(viii) 60 ◦ C. Reprinted with permission from ref. [141]. Copyright 2019 Elsevier.

The electrodeposition of 1D tellurium (Te) nanostructures on the gold surface have

been described in DESs based on ChCl-U and ChCl-EG [141]. The electrocrystallization
followed a 3D-bulk coagulation mechanism with growth control by diffusion. The plating
solution of ChCl-EG and ChCl-U exhibited a sweeping potential between 0.6–1.0 V of cyclic
voltammograms. The Te nuclei and the nanostructure growth were gradually formed on
the substrate in DES mediums (Figure 5b). The surface morphology of Te electrodeposited
films was observed with a uniform distribution of hexagonal Te rods on the Au surface. In
other work, Hammons and coworkers have described using DES for the electrodeposition
of Pd nanoparticles into 2D superstructures [142]. The DES was prepared by recrystallizing
choline chloride and urea (ratio of 2:1). Two temperatures were used for the electrodeposi-
tion process due to their influence on the viscosity and conductivity of the DES. The SEM
characterized the nanoparticle morphology to show large particles of ~20 nm at 44.5 ◦ C
and small particles of ~10 nm at 32.5 ◦ C. The role of DES was confirmed as a stability
agent of the nanoparticles in the electrochemical process. Similarly, direct and pulse current
electrodeposition of Pd from a mixture of DES component and palladium (II) chloride was
reported [143].
The role of DES in triacontahedral Pd nanocrystals (C-DTH Pd NCs) was demon-
strated [144]. The DES took part in the growth of C-DTH Pd NCs by adjusting the square
wave potential’s upper limit. In principle, DESs were excellent soluble solvents for metal
and metal oxides. It was reported that the metal oxides usually are insoluble in common
room-temperature ionic liquids but have high selective dissolution in DES [145]. The elec-
trocrystallization behavior of copper in DES was studied previously [146]. The copper (I)
oxide was introduced into the urea melt by dissolving Cu2 O. The DES performed potential
for inexpensive electroplating of copper warrants a copper salt reaction. In another study,
the preparation of copper nanoparticles (CuNPs) in DES was described [147]. The cyclic
voltammogram analysis was performed to analyze the electroreduction of copper in DES
with a coefficient of 0.78 × 10−8 cm2 s−1 . It was found that depending on the voltage, the
CuNP sizes were increased from 28 ± 7 and 57 ± 6 nm at 2.5 and 2.2 V, respectively. The
ChCl-urea-based DES exhibited a potential replacement of the traditional hydrogen evolu-
tion for fabricating CuNPs. Vertically aligned carbon nanotubes having nano-chromium
magnetic domains were developed using DES [148]. Using chromic acid electroplating for
electrodepositing electronegative metals from an aqueous solution is sufficient. In a eutectic
mixture of ChCl and CrCl3 .6H2 O, chromium’s conformable electroplate nanomagnetic
domains onto carbon nanotube were achieved. Cvetkovic and coworkers have shown
that using DES to control the electrodeposition of aluminum (Al) with Al grains varied in
size from nano- to micro-meters [149]. The usage of DES-based ChCl-U for the electrode-
position of aluminum was addressed [150,151]. The nucleation and growth of Al were
studied in ChCl-U [151]. In another work, gold and silver were recycled from anodic slime
using choline chloride and ethylene glycol (molar ratio of 1:2) [152]. The grain silver and
gold crystals were ~28.04 and 10.5 nm, respectively. Sides and coworkers have presented
nanoscale manganese (Mn) thin films deposited on disk electrodes from a mixture of ChCl
and U [153]. The deposited metallic Mn films were observed with a minimum thickness
of 400 nm and were highly conductive. Mn deposition could be resumed at low current
efficiency [117]. Manuel and coworkers have reported the electrodeposition of FeNPs onto
the electrode surface of HOPG from Fe(III) ions in ChCl-U DES [154]. The electrodeposition
of pure metal and electrochemical synthesis of nanostructure on the surface of electrodes
Nanomaterials 2023, 13, 1164 14 of 29

using DESs has been considered an innovative methodology to control better the size,
morphology, and surface chemical composition of the nanostructure materials.

Table 1. Electrodeposition of nanostructures of metals and alloys with DESs-based choline chloride.

Metal or Alloy Type DES Component Molar Ratio References

Ni Nanoparticle ChCl-EG 1:3 [134]
Ni Nanosheet ChCl-EG 1:2 [135]
ChCl-U 1:2
Ni Nanostructure and nanofilm [136,138,140]
ChCl-EG 1:2
ChCl-U 1:2
Te Nanoparticle [141]
ChCl-EG 1:2
Pd Nanoparticle ChCl-U 1:2 [142]
Pd Nanocrystal ChCl-U 1:2 [143,144]
Fe Nanoparticle ChCl-U 1:2 [154]
Cu Nanoparticle ChCl-U 1:2 [147]
Au-Ag Nanoparticle ChCl-EG 1:2 [152]
Mn Nanofilm ChCl-U 1:2 [153]
Fe-Cr Nanocrystal ChCl-EG 1:3 [155,156]
Cu-Au Bimetallic nanostructure ChCl-U 1:2 [157]
Ni-Mo Nanocrystal ChCl-PG 1:2 [158]
Au-Pt Nanoflower ChCl-EG 1:2 [159]
Ni-Co Nanofilm ChCl-EG 1:2 [160]
Pd-Co Nanoparticle ChCl-U 1:2 [161]
Co-Pt Nanocrystal ChCl-U 1:2 [162]
Ni-Co-Sn Nanocrystal ChCl-EG 1:2 [163]
ChCl: choline chloride, EG: ethylene glycol, U: urea, PG: propylene glycol.

3.3.4. Electrodeposition of Alloys

The electrodeposition and electrochemical behavior of alloys in DESs have been
extensively addressed, such as Fe-Cr [155,156], Cu-Au [157], Ni-Mo [158], Au-Pt [159],
Ni-Co [160], Cu-Sn [164], Zn-Sn [165], Pd-Co [161], and Co-Pt [162]. The electrodeposition
of more than one metal often forms different structures and properties [166,167]. The
electrochemical behavior and process are similar to pure metal deposition. The physical
and chemical character parameters differ with respect to the temperature, composition,
potential, current density, and plating bath. It has been reported that the ultimate aprotic
liquids (e.g., DESs) for the electrodeposition of alloys can avoid the hydrogen evolution
issue that limits the potential application of an aqueous solution [55,140]. Recently, the
nanoscale Fe-Cr alloy was achieved by electrodeposition in ChCl-EG without adding any
additives (Figure 6a) [155,156]. CrCl3 .6H2 O and FeCl2 .4H2 O were dissolved in ChCl-EG
DES. The nucleation of Fe, Cr, and Fe-Cr alloy was more instantaneous. However, the
nucleation of Fe or Cr was less efficient than the Fe-Cr combination, demonstrating the
co-deposition in DES. Notably, a larger concentration ratio of Fe(II) and Cr(III) (i.e., ratios of
1:5–3:3) exhibited high electrodeposition of the nanocrystal alloy. The scratched as-prepared
Fe-Cr alloys comprised a dense surface with a mean diameter of 1.56 nm. The reaction
temperature has significantly impacted the electrical conductivity and viscosity of DESs
which has been discussed above to influence the mobility of ions and the interaction force
between ions [168].
 ChCl-EG DES to obtain a crystallite size of 7–21 nm [163]. By ultimate DESs, alloys’ elec-
trodeposition and the electrochemical process can be controlled to obtain the nanostruc-
tured materials without requiring additives and stabilizing agents. The materials’ prop-
erties depend on the experimental setup, including plating bath composition, current
density,
Nanomaterials 2023, 13, 1164potential, and temperature. Several metals and alloys have been prepared in 15 of 29
DESs to avoid hydrogen evolution reactions.

Figure 6. (a) TEM image

Figure (i)TEM
6. (a) andimage
size (i)
distribution histogram
and size distribution (ii) of (ii)
histogram Fe-Cr alloy
of Fe-Cr fabricated
alloy fabricated in in ChCl-EG
ChCl-EG DES. Reprinted with permission
DES. Reprinted from from
with permission ref. [155]. Copyright
ref. [155]. Copyright 2022
2022Elsevier.
Elsevier.(b)
(b)Preparation
Preparation of Cu-Au
of Cu-Au nanostructures by co-electrodeposition
nanostructures by co-electrodeposition in DES.
in DES. Green
Greenelectrodeposition
electrodeposition ofofCu Cu and
and AuAu high surface
high surface area area
on glassy carbon (GC) in
on glassy carbon (GC) in DES DES (i); FE-SEM images of Au deposit (ii) and Cu de-
FE-SEM images of Au deposit (ii) and Cu deposit (iii); Cu-Au
posit (iii); Cu-Au co-deposit
co-depositin in stationary
stationary conditions
conditions (iv),stirring
(iv), and and stirring
at 200 rpmat (v).
200 Reprinted
rpm (v). from Reprinted
ref. [169].
from ref. [169].
Fabrication of bimetallic nanostructured Cu-Au by co-electrodeposition in DES has
been published as a green synthesis approach (Figure 6b) [169]. Tunable nanostructure
3.4. Electroless Decomposition
and composition were carried out in green ChCl and U to tailor features of the deposits
Electroless (i.e.,
decomposition
size, morphology, is based and onelemental
autocatalysis [171]. Electroless
composition). Different deposition
bath compositionsis a were
chemical processprepared
that depends on the oxidation of chemical compounds and
in the DES solution. The formation of the nanostructure of single Cu and Au the reduc-
tion of metallic andionsbimetallic
[172]. The redox
Cu-Au in DESswere
electrodes for successfully
electroless deposition
obtained in is thea ChCl-U.
versatileTypically,
technique for metalthe broader
plating potential of DESs in electrochemical
and metal-based material development applications relates
[173]. to their negligible
Electroless
hydrogen evolution
deposition methodology and thermal
can be classified intostability on the electrode.
three categories: Niciejewska
galvanic and coworkers
displacement
reaction, reducing agent usage, and disproportionation reaction. Electroless plating baths in DES-
have described a homogenous nanocrystalline structure of Ni-Mo electrocoating
based ChCl-PG [158]. The use of DES can overcome the limit of water-based galvanic baths
typically contain metal ions resource, reducing agents, stabilizers, and buffering agents.
regarding the significant release of hydrogen from the water bath. It was also reported that
In galvanic displacement, the base materials are dissolved in the solvent, and the metallic
the deposited nanocrystals in DES exhibited low surface roughness compared to aqueous
ions are usuallysolutions
reducedand without requiring
sufficient corrosion reducing
resistance agents
[170].[174]. For instance,
In another work, Li and Wang coworkers
and coworker have havedescribed
presented an dipping Au deposition
electrochemical fromofcholine
fabrication chloride and
AuPt nanoflowers chloro- ChCl-
in DES-based
auric acid (ChCl-HauCl
EG [159].4) The [175]. In DES,
one-step the ChCl wasreduction
electrochemical used as awas ligand,
carriedandoutHauCl 4 was
to control and form
bimetallic AuPt alloy nanoflowers. The role of DESs was indicated as solvents and shape-
directing agents. DESs are considered green solvents that have been widely applied in
the reaction process of nanoparticle fabrication. Moreover, the electrodeposition of Ni-Co
alloys was successfully conducted in ChCl-EG DES at room temperature [160]. The Ni-Co
alloys had a cubic structure and refined grains. The grains of deposits were identical
and had a size of about 20 nm. Recently, the fabrication of Pd-Co alloy nanoparticles
Nanomaterials 2023, 13, 1164 16 of 29

(PdCoNPs) has been described to obtain by an electrochemical process in DES-based ChCl-

U [161]. The potentiostat investigated the formation of PdCoNPs on glassy carbon (GC)
electrodes from their precursors dissolved in the ChC-U. The obtained PdCoNPs had an
average size of 30 ± 4 nm and particle number density of (4.23 ± 0.33) × 1010 PdCoNPs
cm−2 . The electrodeposition of Ni-Co-Sn alloy was investigated from ChCl-EG DES to
obtain a crystallite size of 7–21 nm [163]. By ultimate DESs, alloys’ electrodeposition
and the electrochemical process can be controlled to obtain the nanostructured materials
without requiring additives and stabilizing agents. The materials’ properties depend on
the experimental setup, including plating bath composition, current density, potential, and
temperature. Several metals and alloys have been prepared in DESs to avoid hydrogen
evolution reactions.

3.4. Electroless Decomposition

Electroless decomposition is based on autocatalysis [171]. Electroless deposition
is a chemical process that depends on the oxidation of chemical compounds and the
reduction of metallic ions [172]. The redox in DESs for electroless deposition is a versatile
technique for metal plating and metal-based material development [173]. Electroless
deposition methodology can be classified into three categories: galvanic displacement
reaction, reducing agent usage, and disproportionation reaction. Electroless plating baths
typically contain metal ions resource, reducing agents, stabilizers, and buffering agents.
In galvanic displacement, the base materials are dissolved in the solvent, and the metallic
ions are usually reduced without requiring reducing agents [174]. For instance, Wang and
coworker have described dipping Au deposition from choline chloride and chloroauric
acid (ChCl-HauCl4 ) [175]. In DES, the ChCl was used as a ligand, and HauCl4 was the
source of Au. The study revealed a decrease in deposition rate by an increase in ChCl
concentration due to its effect on the viscosity and formation complex with Au(III). The
lower ChCl concentration allowed a shift in equilibrium because the increase of free Au
induced the collision between Ni and Au. In optimized conditions, SEM and XRD obtained
the Au coating layer with a thickness of about 50 nm in DES.
Electroless deposition in DESs has been applied for various surface coatings, such as
pure metals [176–178] and alloys [179,180]. Recently, the electroless deposition of Rhenium
from reline DES-based ChCl-U has been demonstrated [176]. The evaluation of corrosion
performance was tested by voltammetry and chronoamperometry. Similarly, Ni’s electro-
less and electrolytic deposit in DES-based ChCl-EG and ChCl-U has been reported [181].
The cathodic current efficiency of Ni deposition was 97%. Yang and coworkers have pre-
sented N-decorated h-BN powders using ChCl-EG through electroless plating [182]. It was
observed that an increase in Ni plating time and the average size of spheroid Ni particles
ranging from 10–1000 nm caused a high deposition of Ni particles on the h-BN surface. In
another work, electroless Ni-P coating was utilized in DES-based ChCl-EG in wide-range
temperatures to improve the properties of Al alloy in terms of corrosion resistance and me-
chanical features [179]. ChCl-EG was used as deposition media for the Cu dipping layer on
Ai alloy with a hierarchical formation and electroless Ni-P process. The globular protrusion
of the deposited layer was rough and explored numerous nanosized particles. The potential
of ChCl-EG was reported to facilitate sustained galvanic alternative deposition with high
consistency, which is challenging to achieve in an aqueous reaction [177]. The design of
immersion plating from DESs relies on the potential galvanizing alteration between the ions
and the substrate. The reduction of metal base material in DES occurred with or without
reducing agents. The electroless process by simple immersion of the substrate in DESs con-
tains metal ions base materials, and homogenous film can be deposited fast [19]. In some
cases, a neutral plating bath triggered by DESs could minimize the likelihood of corrosion
occurring and reduce the possible formation of black-pad caused by excessive corrosion.
Nanomaterials 2023, 13, 1164 17 of 29

3.5. Nanostructure Functionalization

The process of adding new functional groups to the surface of the materials via
chemical or physical interaction is called functionalization [183,184]. DESs have been
recognized as functionalization agents for nanomaterial engineering. Due to the various
combinations and molar ratios of HBA and HBD of DES, different interaction types, such as
weak, non-covalent, anion exchange, and π-π/hydrogen bonding takes place to contribute
to the properties of functional medium [185,186]. This phenomenon could create the unique
interaction of DES and target compound, making it a potential application in synthetic
chemistry and material functionalization [187]. In polymer-based materials, DESs can
be used as a functional additive that acts as a template and/or ligand supplier [55,188].
Several ChCl-based DESs have been designed to be used as plasticizers for producing
polymers [189–192]. DESs functionalized polymers have been reported for easy and efficient
biocatalysis [193]. The poly(vinyl pyrrolidone DES)s were obtained to determine the best
L-asparaginase absorption. In another work, Ni and coworkers have described magnetic
carbon nanotube (M-CNT) modified polymeric DES (PDES) for solid-stage extraction of
bovine serum albumin (Figure 7a) [194]. Acrylic acid was used to modify M-CNT, resulting
in M-CNT@AA coated with the designed DES by free radical copolymerization. After the
functionalization of the DES polymer layer, a reduction from 52.89 to 43.72 emu/g of the
magnetic strength of the magnetic nanoparticle was observed.
More reports have described the functionalization of CNT using DESs [195–198].
Alomar and coworkers studied DESs composed of ChCl and six different HBDs to use
as functionalization agents on CNT for heavy metals absorption [195]. DESs have been
successfully applied for multi-wall CNT (MWCNT) functionalization with significantly
improved MWCNT structure and chemical properties. Several different designed DESs
were prepared and studied. To study electrochemical sensing, the ChCl-U functionalized
MWCNT was applied [196]. Similarly, DES, comprised of allyl triphenyl phosphonium
bromide and glycerol, has been prepared to modify CNT as a novel absorbent of mercury
from water [197]. The DES functionalized nanostructure significantly enhanced their
stability and good dispersion in the target solvents. The effects of DESs on the surface of
CNT were intensively investigated [198]. In this work, novel absorbents were created from
DESs and CNT to remove arsenic ions (As3+ ). Specifically, active sites on the CNT surface
and adsorption of As3+ were enhanced in the presence of DESs.
Applying DESs for graphene oxide functionalization and nanoparticle conjugation
has recently been investigated and applied in drug delivery, water treatment, catalysis, and
biosensor application [199,200]. The modification and addition of functional groups to the
surface of graphene were investigated with eighteen different types of ammonium- and
phosphonium-salt-based DESs [200]. The study indicated the change in the surface chem-
istry of materials after DES functionalization according to the new hydrophilic functional
groups and different reducing abilities of the used DESs. In another work, DES-based
ChCl and U have been used to control the Fe3 O4 conjugate in graphene oxide (GO) (Fig-
ure 7b) [199]. The nanohybrid DES/GO-Fe3 O4 exhibited good characteristics of organic
dye absorbents. The study indicated that the conjugation probably occurred due to DES’s
rendering of chemical bonds rather than physics interaction. Using DES as a functional
medium, high uniformity and narrow size distribution of FeNPs in the nano-hybrids were
obtained. Recently, the behavior absorbs layer of ionic surfactants (sodium dodecyl sulfate
(SDS) and cetyltrimethylammonium bromide (CTAB) in DESs (ChCl-EG and ChCl-Gly)
have been studied to indicate the new role of DESs in functionalization process [201]. In
both as-prepared DESs, SDS was completely desorbed, whereas CTAB remains absorbed at
positive and negative potentials. The stronger solvophobic interaction alkyl chains in DESs
allowed low-concentrated CTAB self-assemble into a robust coating. Since different effects
of surfactants on the electrochemical response of DES/electrode structure are explored,
choosing a suitable surfactant is essential to ensure effective adsorption and desorption
work. Typically, using DESs as functionalization agents through conjugation ligands sup-
plier or new functional group addition improves the nanomaterials’ stability, dispersibility,
 Nanomaterials 2023, 13, 1164 18 of 29

Nanomaterials 2023, 13, x FOR PEER REVIEW 19 of 31

and properties. The particular combination of DESs and additive surfactants can improve
the materials’ target chemical and physical characteristics.

Figure
Figure7. 7.(a)(a)Schematic
Schematic illustration
illustration ofof
thethe fabrication
fabrication process
process of magnetic
of magnetic carboncarbon
nanotubes nanotubes
modified modi-
fied
with polymeric DES (M-CNT@PDES) and its design application for extraction of bovinebovine
with polymeric DES (M-CNT@PDES) and its design application for extraction of serumserum
albumin (BSA). TEM images of CNT (i), M-CNT (ii), and M-CNT@PDES
albumin (BSA). TEM images of CNT (i), M-CNT (ii), and M-CNT@PDES (iii). Reprinted with (iii). Reprinted with per-
mission from ref. [194]. Copyright 2020 Elsevier. (b) Schematic illustration of
permission from ref. [194]. Copyright 2020 Elsevier. (b) Schematic illustration of the conjugation the conjugation of
magnetic nanoparticles
of magnetic (MNPs)
nanoparticles (MNPs) onto
ontographene oxide(GO)
graphene oxide (GO)using
using ChCl-U
ChCl-U andand its application
its application for for
lead(II) and
lead(II) andmethylene blueremoval.
methylene blue removal. Inset
Inset TEMTEM
imageimage ofGO
of bare bare GO nanosheets
nanosheets and DES function-
and DES functionalized
alized GO nanosheets
GO nanosheets (DES@GO).
(DES@GO). Reprinted
Reprinted with permission
with permission fromCopyright
from ref. [199]. ref. [199].2020
Copyright
Elsevier.2020 Else-
vier.
3.6. DES-Based Nano-Catalytic System
3.6. DES-Based Nano-Catalytic
The nano-catalytic System DESs have been described. DES can be utilized to
system-based
The nano-catalytic
immobilize system-based
the nanostructures or supportDESs have been
interactions described.
of the DES can
catalytic system andbe utilized to
enhance
immobilize the nanostructures or support interactions of the catalytic systemwas
the catalytic activity. The first catalytic-based DES platform for organic transformation and en-
hance the catalytic activity. The first catalytic-based DES platform for organic transfor-
mation was reported by Zamani and coworkers [202]. The magnetic nanoparticle (MNPs)
anchored DESs were used for catalysis. The reusable catalyst system included a
DESs-based ChCl and ρ-toluene sulfonic acid (ρTSA) covalently adsorbed on MNPs with
Nanomaterials 2023, 13, 1164 19 of 29

reported by Zamani and coworkers [202]. The magnetic nanoparticle (MNPs) anchored
DESs were used for catalysis. The reusable catalyst system included a DESs-based ChCl
and ρ-toluene sulfonic acid (ρTSA) covalently adsorbed on MNPs with a size of 12 ± 2 nm.
It was indicated that the bonding of ChCl of DES to the MNPs surface increased the
catalytic activity of DES. Previously, ion-exchange resin Amberlyst 15 induced dehydration
of fructose and sucrose in eight DES has been explored [203]. The eight prepared DESs
differed by their HBA and HBD. Generally, a distinctly beneficial effect of coupling Aberlyst
15 with dicarboxylic acid-based DES was observed. The structure of DES components
affected the reaction process to influence HBD. The ChCl-GA DES performed the best
cooperation and balance between catalytic ability and stability. Recently, the combination
of reline DES, gold nanoparticles (AuNPs), and Titanium oxide (TiO2 ) was developed as
a new catalysis system [204]. The reline DES and AuNPs supported TiO2 nanoparticles
were investigated with great prominence in various sections of oxidation for catalyzing
reactions. Similarly, reline is combined with the magnetic nanocatalyst as a green and
reusable solvent.

3.7. DES-Based Nanofluidic System

Recently, nanofluids have been applied for heat transfer applications where nanoparti-
cles and ionic liquids (ILs)/DESs have been utilized [205–208]. In particular, DESs -a new
generation of ILs- have been extensively investigated to prepare nanofluids, which are
economical, eco-friendly, and biodegradable [23,209–211]. Besides, some common nanopar-
ticles (e.g., copper, silica, magnesium oxides), carbon nanotubes (CNT), or graphene have
been used for synthesizing nanofluids [212,213]. For example, Liu et al. suggested us-
ing a chemically decorated silica nanoparticle (SiO2 ) filled DES to improve the thermal
conductivity and static stability of the synthesized nanofluids in energy transfer appli-
cations (Figure 8a) [214]. The silica nanoparticles were modified with copper, resulting
in an enhanced thermal conductivity of silica nanoparticle (SiO2 ) filled DES nanofluids
(13%). Walvekar and coworkers introduced the DES-carbon nanotube (CNT)-nanofluids
by dispersing CNT into DESs using an ultrasonic technique without any stabilizer [208].
The authors found that the dispersion of CNT in DESs enhanced the thermal stability
of DES-CNT-nanofluids, and these synthesized nanofluids had a lower freezing point
and vapor pressure than ethylene glycol (EG) and triethylene glycol (TEG). Fan et al. de-
scribed a superparamagnetic nanofluid based on a ChCl/1-(0-tolyl)biguanide DES for
identifying perfluoroalkyl substances in edible oils (Figure 8b) [215]. For the microextrac-
tion of perfluoroalkyl substances (PFASs), the nanofluid acted as a sorbent material that
exhibited high sensitivity (detection limit: 0.3–1.6 pg g−1 ) with a simple and rapid test
for the enrichment and determination of trace PFASs. For H2 S removal performances, a
nanofluid system containing DESs and Cu nanoparticles was used with excellent outcomes
for H2 S removal (Figure 8c) [216]. The high regeneration performance of non-aqueous
nanofluid systems was also observed. In addition, there are several studies on choline
chloride and ethylene glycol–based DES for synthesized nanofluids for energy transporta-
tion [217,218]. Liu and coworkers used the combination of ChCl-EG DES as the based
solvent and silica-decorated graphene for improving the stability of nanofluids, with 11.26%
thermal conductivity enhancement [219]. Jafari et al. presented some new nanofluids based
on DESs (Figure 8d) [220]. In this study, to prepare nanofluidics, four different DESs were
used for dispersing MgO nanoparticles, and thermal conductivity was almost constant.
Recently, DES ChCl-based nanofluids were formed by dispersion of nano-TiO2 , Fe2 O3 ,
CuO, SiC, and carbon. These nanofluids exhibited an increase in thermal conductivity
and heat capacity up to 4.23 and 26.23%, respectively [221]. In conclusion, DES-based
nanofluids demonstrated potential prospects in the low-grade thermal energy utilization
fields, specific heat capacity, thermal conductivity, and wide working temperature ranges.
Nanomaterials
Nanomaterials 2023,13,
2023, 13,1164
x FOR PEER REVIEW 20 of
21 of 31 29

Figure 8.8. (a)

Figure (a) Schematic
Schematic representation
representationofofthethesilica-filled
silica-filledDES-based
DES-basednanofluids
nanofluids forfor
energy
energytrans-
trans-
portation. Reprinted with permission from ref. [214]. Copyright 2019 American
portation. Reprinted with permission from ref. [214]. Copyright 2019 American Chemical Society. Chemical Society.
(b) Pretreatment procedure by using DES-based superparamagnetic nanofluid. Reprinted with
(b) Pretreatment procedure by using DES-based superparamagnetic nanofluid. Reprinted with per-
permission from ref. [215]. Copyright 2021 Elsevier. (c) Scheme of utilizing of DES-based nanoflu-
mission from ref. [215]. Copyright 2021 Elsevier. (c) Scheme of utilizing of DES-based nanofluidic
idic system and Cu nanoparticles for enhancing hydrogen sulfide removal. Reprinted with per-
system
missionand fromCuref.
nanoparticles for enhancing
[216]. Copyright hydrogen
2021 Elsevier. sulfide removal.
(d) Graphical illustrationReprinted with permission
of the fabrication pro-
from ref.of[216].
cedure DES Copyright
and design2021 Elsevier. (d)
of DES-based GraphicalReprinted
nanofluids. illustration
fromof the
ref. fabrication
[220]. procedure of DES
and design of DES-based nanofluids. Reprinted from ref. [220].
4. Conclusions
4. Conclusions
This review summarizes the significant potential of DESs in nanomaterial fabrica-
tion.This reviewthe
Currently, summarizes
publications theand
significant potential
applications of DESsof DESs in nanomaterial fabrication.
in chemical/electrical reactions
Currently, the publications and applications of DESs in chemical/electrical
have been growing fast, especially in nanostructure fabrication, due to their reactions
abilityhave
to
been growing
overcome the fast, especially
challenges in nanostructure
of conventional fabrication,
solvents, such as due to their ability
the hydrogen to overcome
evolution issue
the challenges
of an aqueousofsolution.
conventional solvents, such
The considerable as the hydrogen
potential of DESs in evolution issue
fabricating of an aqueous
various nano-
solution.
materials The
and considerable potential
nanomaterial-based of DESs
systems has in
beenfabricating
studied; various
however,nanomaterials
the use and de- and
nanomaterial-based
sign of DESs in developing renewable materials and nano-based systems such as micro-in
systems has been studied; however, the use and design of DESs
developing
fluidic devicesrenewable
and chipsmaterials
are stilland nano-based
limited and need systems such as microfluidic
to be explored to open up devices
new hori-and
chips are still limited and need to be explored to open up new
zons of new nanotechnology techniques and approaches. Additionally, the physiochem- horizons of new nanotech-
nology techniques
ical properties and approaches.
of DESs Additionally,
can be controlled the physiochemical
by fine-tuning HBAs and HBDs properties of DESs
components.
can be controlled by fine-tuning HBAs and HBDs components. Their
Their attributes of the high solubility of the polymer and other chemical substances allow attributes of the
high solubility of the polymer and other chemical substances allow
DESs based fabrication strategies. They are applied in various roles, such as reaction DESs based fabrication
strategies. They are
media, catalysts, applieddirection,
structure in various roles, such control,
morphology as reactionandmedia, catalysts,
assembly support,structure
con-
direction,
tributing tomorphology
sustainablecontrol, and assembly
nanostructure support,
engineering. Thiscontributing to sustainable
provides opportunities for nanos-
nan-
tructure engineering.
otechnology to meet theThis provides
circular opportunities
economy, for nanotechnology
and a large amount of related toresearch
meet thewill
circular
be
economy, and a large amount
a breakthrough in the future. of related research will be a breakthrough in the future.

Author Contributions:Conceptualization,
AuthorContributions: Conceptualization,N.N.N., H.D.K.D.,
N.N.N., N.Y.L.N.Y.L.,
H.D.K.D., and K.T.L.T.;
and writing—original
K.T.L.T.; writ-
draft preparation,
ing—original N.N.N.,
draft H.D.K.D.
preparation, and K.T.L.T.;
N.N.N., writing—review
H.D.K.D., and K.T.L.T.; and editing, N.Y.L.
writing—review andediting,
and K.T.L.T.;
supervision, N.Y.L. and
N.Y.L. and K.T.L.T.; K.T.L.T.; N.Y.L.
supervision, projectand
administration, N.Y.L.;
K.T.L.T.; project funding acquisition,
administration, N.Y.L.ac-All
N.Y.L.; funding
authors have
quisition, readAll
N.Y.L. and agreedhave
authors to the published
read version
and agreed to theofpublished
the manuscript.
version of the manuscript.
Nanomaterials 2023, 13, 1164 21 of 29

Funding: This research was supported by the Basic Science Research Program through the Na-
tional Research Foundation of the Republic of Korea (NRF), funded by the Ministry of Education
(2021R1A6A1A03038996) and also by Korea Basic Science Institute (National Research Facilities and
Equipment Center) grant funded by the Ministry of Education (2020R1A6C101A184).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: No new data were created or analyzed in this study. Data sharing is
not applicable to this article.
Conflicts of Interest: The authors declare no conflict of interest.

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