Materials 13 03485

materials
Review
Advances in Ultrasonic Spray Pyrolysis Processing of
Noble Metal Nanoparticles—Review
Peter Majerič 1,2 and Rebeka Rudolf 1,2, *
1 Faculty of Mechanical Engineering, University of Maribor, Smetanova Ulica 17, 2000 Maribor, Slovenia;
peter.majeric@um.si
2 Zlatarna Celje d.o.o., Kersnikova 19, 3000 Celje, Slovenia
* Correspondence: rebeka.rudolf@um.si

Received: 14 June 2020; Accepted: 5 August 2020; Published: 7 August 2020
Abstract: In the field of synthesis and processing of noble metal nanoparticles, the study of the
bottom-up method, called Ultrasonic Spray Pyrolysis (USP), is becoming increasingly important.
This review analyses briefly the features of USP, to underline the physical, chemical and technological
characteristics for producing nanoparticles and nanoparticle composites with Au and Ag. The main
aim is to understand USP parameters, which are responsible for nanoparticle formation. There are
two nanoparticle formation mechanisms in USP: Droplet-To-Particle (DTP) and Gas-To-Particle (GTP).
This review shows how the USP process is able to produce Au, Ag/TiO2 , Au/TiO2 , Au/Fe2 O3 and
Ag/(Y0.95 Eu0.05 )2 O3 nanoparticles, and presents the mechanisms of formation for a particular type of
nanoparticle. Namely, the presented Au and Ag nanoparticles are intended for use in nanomedicine,
sensing applications, electrochemical devices and catalysis, in order to benefit from their properties,
which cannot be achieved with identical bulk materials. The development of new noble metal
nanoparticles with USP is a constant goal in Nanotechnology, with the objective to obtain increasingly
predictable final properties of nanoparticles.
Keywords: Ultrasonic Spray Pyrolysis; Nanotechnology; noble metals nanoparticles; formation

mechanism; characterisation; properties
1. Introduction
The processing of aerosols (solid or liquid particles suspended in gas) and obtaining various types
of fine particles and nanomaterials from aerosols has been known for a long time. These materials are
meant for diverse uses in different fields, from nanomedicine, sensing applications, electrochemical
devices, catalysis, energy conversion and storage, to name a few [1–4]. Generally, the basic principle
of aerosol formation arises from a solution that contains dissolved material (usually salts of various
metals)—which are commonly called precursors. In the synthesis, the powder product is atomised
from an aerosol composed of liquid droplets, which are then transported with a carrier gas to the reactor
where the chemical transformation occurs. The chemical composition of the precursor depends on the
chemical composition of the fine powder we want to obtain and the type of processing method used,
such as spray drying, Spray Pyrolysis, Flame Spray Pyrolysis, thermal decomposition, micronisation
or gas atomisation [5–7].
Spray drying techniques are used widely in the food industry, such as for the production of milk or
fruit powders and for flavour ingredients, as well as in pharmaceutics’ production [5,8]. This technique
is a low-cost, environmentally friendly method with proven scalability, and is well known in Chemical
Engineering [9].
Spray Pyrolysis, Flame Spray Pyrolysis and aerosol decomposition or thermolysis, generally
involve atomisation of metal salt solutions as the precursor for the final metal or metallic oxide particles,
Materials 2020, 13, 3485; doi:10.3390/ma13163485 www.mdpi.com/journal/materials

Materials 2020, 13, 3485 2 of 28
and subjecting these liquid droplets to a high temperature in a furnace or a flame. Water or organic
solutions with different metal salts may be used, from chlorides, acetates, nitrates, bromides, sulphides,
hydroxides, etc., depending on the necessary composition and structure of the final particles [5,10].
Aerosol assisted sol–gel processes combine the sol–gel chemistry with aerosol processing [11].
In principle, each aqueous aerosol droplet may be used as a single, micron-sized sol–gel reactor,
capable of producing different particle structures, such as mesoporous particles of various materials
and chemical compounds [12–14]. In gas atomisation, liquid metal is sprayed through a nozzle and
cooled rapidly to produce solid small spherical particles of the used metal or alloy [6,7].
Most of these techniques require the atomisation of a liquid solution into micron-sized droplets.
The generation of such droplets is achievable by using pressure, electrostatic fields, centrifugal force or
ultrasound [5].
This review is focused on Ultrasonic Spray Pyrolysis (USP), which combines the ultrasound
used for dispersing the precursor solution into droplets and chemical decomposition of the dissolved
material inside the droplets at elevated temperatures, resulting in the formation of fine powder. In the
USP reactor the evaporation of solvent from droplets occurs first, in the next stage the remaining solvent
inside the dry droplets is decomposed chemically via pyrolysis, and, in the final stage, fine particles are
obtained through the sintering process. The advantage of the USP method is the simplicity of setting
up individual process segments and changing their configuration, continuous nanomaterials’ synthesis,
and the possibility of synthesising nanoparticles from various raw materials. The disadvantage is the
low efficiency, due to losses of the dissolved material on the construction elements of the USP device.
Currently, there is a need for scaled-up production of nanoparticles, able to take up the increasing
quantities of nanoparticles required for advanced applications. Technologies for generating nanoparticle
powders and suspensions have existed for several decades [15], and are being improved upon
continually, while novel approaches are also being studied [16,17]. One potentially reliable method
for the large scale synthesis of nanoparticles is the USP process [18]. This process is considered to
be relatively cost-effective, and easily scalable from the laboratory to an industrial level. Several
different types of nanoparticles and structures can also be produced by USP, such as solid or hollow
nanoparticles, core–shell and ball-in-ball structures, etc. [4,19–22], giving an additional advantage
to this production method. Yolk–shell-structured [23,24], mesoporous [25] and multicomponent
composite particles [26,27] were also proven to be synthesised with this method, by a group focusing
on Li-ion and Na-ion battery applications of these particles. Depending on the particle composition,
the formation of mesoporous or multicomponent structures can also be facilitated with subsequent
processing of the initial particles produced by USP. The process is also used extensively for thin
film deposition [21,28], with multiple layers [29]. The latest scientific finding reported [30] that a
fully solution-based fabrication process exploiting USP and spin coating techniques, owing to their
simplicity, high degree of freedom for mixing metal oxide precursor salts, and larger area deposition,
opens the potential application of solution-processed transistors for low-cost electronic devices.
In our long-term investigation and experimental work, we have used USP to produce several
metallic and metal oxide particles with micron and nano sizes, ranging from Au (from Au salts and from
gold scrap), Ag, Ag/TiO2 , Au/TiO2 , ZnO, Fe/Au, Co, Cr and rare earth metals. For Au nanoparticles
(AuNPs) we have also investigated extensively the cytotoxic and immunomodulatory properties of
these particles for biomedical applications [31–33], as well as their behaviour when exposed to in situ
heating during TEM observation [34], and their use in printing inks for Electronics (not yet published).
We have also applied Au and ZnO nanoparticles in PMMA composites for advanced dental materials
for removable prostheses [35]. The Ag/TiO2 and Au/TiO2 particles were produced for use as catalysts,
and rare earth metals for photocatalytic applications [36,37].
In this review, we outline the advances and insights made on the USP process, obtained through
theoretical and experimental investigations on the addressed materials, completed over the years.
Furthermore, we search literature from the database—the last search was done on 12 May 2020.
This overview contributes to a more comprehensive understanding of this process for similar endeavours
Materials 2020, 13, 3485 3 of 28
on the USP technique, and demonstrates the synthesis and characterisation of some characteristic
nanoparticles through USP.
2. Ultrasonic Spray Pyrolysis

The main elements of the conventional USP device are the ultrasonic generator or nebuliser,
the reactor furnace, and a system for nanoparticle collection and cooling (Figure 1). Ultrasonic
nebulisers are the most efficient amongst other types of nebulisers for nanomaterial production,
such as pneumatic and electrostatic, while also being affordable and having a low droplet velocity.
Pneumatic nebulisers produce droplets by expanding a pressurised liquid. These nebulisers have
a high droplet output of large sizes around ≈50 µm, and the droplet sizes and size distribution are
difficult to control [38]. Electrostatic nebulisers use an electrostatic field to extract droplets from a
liquid [28]. They have a low productivity, and can only be used on conductive liquids. Ultrasonic
nebulisers produce droplets in a narrow size distribution, less than 10 µm, with acceptable productivity.
Ultrasonic spray nozzles generate more stable and uniform droplets, but cannot produce droplets as
small as ultrasonic nebulisers [38]. As such, ultrasonic nebulisers have good characteristics regarding
their droplet output, and are used commonly in Spray Pyrolysis processes (Table 1).
Table 1. Comparison of production yields of selected aerosol routes for particle synthesis.
Particle Production Method Typical Particle Sizes Possible Production Yield

Nanometer to micron-sized particles,
Ultrasonic Spray Pyrolysis 0.1–100 kg/d [28,39]
10 nm–5 µm
Nanometer to submicron-sized particles,
Flame Spray Pyrolysis 1–25 kg/d, derived from [40]
5–500 nm
Spray Pyrolysis—pneumatic nebuliser Micron-sized particles or larger, >1 µm >5 t/d [28]
Spray Pyrolysis—electrostatic nebuliser Nanoparticles, <100 nm <1 kg/d [28]
The sizes of the synthesised nanoparticles depend on the ultrasound frequency [4,41,42], which
determines the sizes of the aerosol droplets and the concentration of the dissolved salts in the
precursor solution droplets. Due to vibrations of the ultrasound below the solution surface, the kinetic
energy of the solution molecules increases rapidly. This causes small droplets to overcome the
surface tension and break away from it. This effect, known as nebulisation (Figure 1), produces
micron-sized aerosol droplets, which act as individual chemical reactors when subjected to thermal
treatment [43,44]. Droplets in a size distribution from 1 to 15 µm are created with a high-frequency
ultrasound (0.5–3 MHz) [45].
The generated droplets of the precursor solution are transported into the furnace with a carrier
gas, where the synthesis stages of evaporation and droplet shrinkage, thermal decomposition and
densification take place. Depending on the precursor salt composition and chemistry, a reaction gas
may be included with the carrier gas, in order to promote the formation of pure metal or metal oxide
nanoparticles. The process forms solid, nonporous nanoparticles with different amounts of aggregation,
depending on the process conditions and parameters used (reaction temperature, gas flow, residence
time, precursor selection and concentration).
Materials 2020, 13, 3485 4 of 28
Materials 2020, 13, x FOR PEER REVIEW 4 of 28
Figure 1.1. Aerosol

Figure Aerosol droplet
droplet formation
formation from
from aa starting
starting solution
solution with
with ultrasound,
ultrasound, an
an example
example of
of gold
gold
chloride precursor for AuNP synthesis (Assumption: The ion states inside the aerosol droplets
chloride precursor for AuNP synthesis (Assumption: The ion states inside the aerosol droplets are the are the
sameas
same asininthe
thestarting
startingsolution,
solution,adapted
adaptedfrom [46,47]).
from[46,47]).
The classification
One generated droplets of the precursor
for nanoparticle synthesis solution are transported
processes is based on into the furnace
the physical statewith
froma which
carrier
gas,nanoparticles
the where the synthesis stages
are formed: Fromof the
evaporation
gas, liquid and droplet
or solid shrinkage,
state. Dependingthermal
on thedecomposition
type of precursor and
densification
and take place. Depending
material synthesised, USP can beon the precursor
categorised salt
in all composition
three states, as and chemistry,can
nanoparticles a reaction
be formedgas
may be included with the carrier gas, in order to promote the formation of pure
from the gas or the liquid/solid state. Depending on the physical state from which nanoparticles are metal or metal oxide
nanoparticles.
formed with USP,Thethereprocess
are two forms solid,main
well-known nonporous
conversion nanoparticles within different
routes described amounts
the literature of
[4,18,48]:
aggregation,
the depending(DTP)
Droplet-To-Particle on the process
and conditions(GTP)
Gas-To-Particle and parameters
conversionused (reaction These
mechanisms. temperature, gas
formation
flow, residence
mechanisms cantime,
bothprecursor selection
occur during and concentration).
synthesis with USP, and are determined by the various USP
One classification
parameters—aerosol for nanoparticle
droplet synthesis
size, gas flow, reaction processes is based
temperatures, on the physical
precursor solutionstate fromsolvent
salt and which
the nanoparticles are formed: From
volatility (ease of vapourisation), etc. the gas, liquid or solid state. Depending on the type of precursor
and material synthesised, USP can be categorised in all three states, as nanoparticles can be formed
USP
fromParameter
the gas orSelection
the liquid/solid state. Depending on the physical state from which nanoparticles are
formed with USP, there are
The size of the obtained two well-known
nanoparticles main
is related conversion
to the routes and
droplet diameter described in concentration
the initial the literature
[4,18,48]:
of the Droplet-To-Particle
the precursor solution. Increasing(DTP)the andultrasonic
Gas-To-Particle
frequency (GTP) conversion
reduces mechanisms.
the droplet diameter These
of
formation mechanisms can both occur during synthesis with USP, and are determined
the produced aerosol, and also increases the ratio of smaller nanoparticles in the final product. by the various
USPformation
The parameters—aerosol
of dropletsdroplet size, gaswas
by ultrasound flow,first
reaction temperatures,
described by Woodprecursor
and Loomis solution
in 1927salt[49].
and
solvent
In 1962, volatility (ease of vapourisation),
Lang formulated etc.
an equation to describe the connection between the ultrasonic frequency
and the mean droplet diameter [50]. A theoretical equation for the prediction of sizes of obtained
USP Parameter Selection
nanoparticles was formed in previous work [51], combining Kelvin’s equation and an equation based
on theThe capillary
size of theory.
the obtained nanoparticlessis related to the droplet diameter and the initial
concentration of the precursor solution. Increasing 3 8·π·γ·C thesolultrasonic
·Mmat
! frequency reduces the droplet
diameter of the produced aerosol, and=also
Dmat 0.34·increases 2the ratio of smaller nanoparticles in the final
ρsol · f ·ρmat ·Msol
(1)
product. The formation of droplets by ultrasound was first described by Wood and Loomis in 1927
D mat isIn
[49]. the1962,
final Lang
particle diameter; C
formulated an ρsol and Mtosol describe
sol ,equation the solutethe concentration,
connection density
betweenandthemolar mass;
ultrasonic
M mat and ρ mat are the molar mass and density of the desired material.
frequency and the mean droplet diameter [50]. A theoretical equation for the prediction of sizes of
In thisnanoparticles
obtained equation, thewas sizeformed
of the nanoparticle
in previous work depends [51],mainly on theKelvin’s
combining diameter of the droplet
equation and an
(frequency of the ultrasonic atomiser)
equation based on the capillary theory. and on the desired material concentration of the precursor
solution. Unfortunately, the coalescence of the droplets is difficult to prevent, and the calculated
mean droplet diameter was expected to be somewhat 8 ∙ ∙ smaller
∙ ∙ than the actual size of the droplets
= 0.34 ∙ (1)
∙ ∙ ∙
is the final particle diameter; , and the solute concentration, density and molar
mass; and are the molar mass and density of the desired material.
In this equation, the size of the nanoparticle depends mainly on the diameter of the droplet
(frequency
Materials 2020,of
13,the
3485ultrasonic atomiser) and on the desired material concentration of the precursor
5 of 28
solution. Unfortunately, the coalescence of the droplets is difficult to prevent, and the calculated
mean droplet diameter was expected to be somewhat smaller than the actual size of the droplets in
in the performed experiments. In the mentioned equation, there is also no account for the effect
the performed experiments. In the mentioned equation, there is also no account for the effect of
of temperature on nanoparticle size. An example of calculating nanoparticle size is given for the
temperature on nanoparticle size. An example of calculating nanoparticle size is given for the
production of AuNPs with an ultrasound frequency of 0.8 and 2.5 MHz in Figure 2.
production of AuNPs with an ultrasound frequency of 0.8 and 2.5 MHz in Figure 2.
450
400
350
2,5 MHz
Particle diameter (nm)
300
250 0,8 MHz
200
150
100
50
0
0 5 10 15 20 25
Precursor concentration (g/l)
Figure
Figure 2.
2. AuNP
AuNP size
size calculations
calculations for
for increasing
increasing gold
gold concentration
concentration in
in the
the precursor
precursor solution,
solution, for
for an
an
ultrasound frequency of 0.8 and 2.5 MHz.
ultrasound frequency of 0.8 and 2.5 MHz.
A
A concentration
concentration of of Au between
between 1 and 20 g/L was was selected
selected for
for this
this calculation.
calculation. Hence,
Hence, for for an
an
ultrasonic
ultrasonic frequency
frequency of of 0.8
0.8 MHz,
MHz, the the calculated
calculated mean mean AuNP
AuNP diameter
diameterrangedrangedfrom from150 150 toto 407
407 nm.
nm.
Increasing
Increasing the the frequency
frequencyup uptotof f==2.5
2.5MHz,
MHz,the the calculated
calculated mean
mean particle
particle diameter
diameter waswas between
between 70 and70
and 190 nm.
190 nm. The The increase
increase in frequency
in frequency resulted
resulted in smaller
in smaller dropletdroplet diameter
diameter and and smaller
smaller nanoparticle
nanoparticle size.
size. In practical terms, the aerosol droplets are actually generated in a size distribution, rather than in
In practical
a single terms, the theoretical
size; however, aerosol droplets are actually
calculations provide generated
a good in a size point
starting distribution, rather than
for the selection of
in
thea precursor
single size; however, theFor
concentration. theoretical calculations
a more exact provideofa the
determination good starting
aerosol point for
droplets, thediffraction
laser selection
of the precursor
measurements areconcentration. For a more
needed of the produced exact
aerosol determination
mist of the aerosol
[45]. As an example, theoreticaldroplets, laser
calculations
diffraction measurements are needed of the produced aerosol mist [45].
predicted a size of 193 nm for gold nanoparticles with a 0.8 MHz ultrasound, and 91 nm with a 2.5 MHz As an example, theoretical
calculations
ultrasound. The predicted a size ofresults
experimental 193 nm for gold
showed nanoparticles
a size range fromwith a 0.8
38–200 nm MHz ultrasound,
for 0.8 MHz and and 10–25091 nmnm
with
for 2.5a 2.5
MHz MHz [46].ultrasound.
The aerosol The experimental
collisions, droplet results showed a size
size distribution andrange from 38–200
gas-phase formation nm are for not
0.8
MHz and in
included 10–250 nm for 2.5 calculation.
the theoretical MHz [46]. The aerosol collisions,
However, droplet
the calculations size
are distribution
still adequate to andbegas-phase
used as a
formation
guideline for are the
notselection
includedof inprecursor
the theoretical calculation. However, the calculations are still adequate
concentration.
to be The
usedselected
as a guideline
reactionfor the selectiondepend
temperatures of precursor
on theconcentration.
decomposition temperatures of the precursor
The selected
components. reaction to
In relation temperatures
gas flow, the depend on the decomposition
temperature profile along the temperatures
length of the of the precursor
reaction tube
components.
changes—thisInneeds relationto beto considered
gas flow, the temperature
while designingprofile along theof
the production length of the reaction
nanoparticles, so thattube the
changes—this needs to be considered while designing the production of
residence time of the particles allows for the total decomposition to be carried out, with no unreacted nanoparticles, so that the
residence
particles in time
theof the product.
final particles allows
As such, forthe
theresidence
total decomposition
time, and the to be carriedofout,
velocity thewith
aerosolno unreacted
inside the
particles in thealso
reaction tube, finaldepend
product. on Asthesuch, the residence
tube diameter. The time, and tube
gas flow, the velocity
diameter ofand
the length
aerosolalsoinside the
dictate
reaction tube,
the velocity also depend
profile on the tube
and temperature diameter.
profile acrossThe the gas flow, tubeofdiameter
cross-section the tube,and as islength
knownalso from dictate
fluid
the velocityTubes
dynamics. profile of and
largertemperature
diameters and profile
shorteracross the cross-section
lengths of the tube,
have an undeveloped gas as is known
flow, from
while longer
fluid
tubesdynamics.
with smaller Tubes of larger
diameters have diameters and shorter
a more developed lengths
flow, haveinanFigure
as shown undeveloped
3. The shortgas tube
flow,lengths
while
longer tubes 3with
from Figure smaller not
are usually diameters
used with have a more
USP, developed
but the velocity flow,
profileasaspect
shownis in Figure 3.toThe
important short
consider
when selecting the gas flow, residence time and temperature parameters, which dictate whether the
aerosol will transform fully into the desired particles.
tube lengths from Figure 3 are usually not used with USP, but the velocity profile aspect is important
to consider
Materials 2020, when
13, 3485selecting the gas flow, residence time and temperature parameters, which dictate
6 of 28
whether the aerosol will transform fully into the desired particles.
Figure 3. The
Figure 3. Thegas
gasvelocity
velocity profile
profile in the
in the reactor
reactor tubetube
for a for a laminar
laminar flow, depending
flow, depending on the
on the tube tube
diameter
diameter and length, with a representation of the temperature profile along the length
and length, with a representation of the temperature profile along the length of the tube. of the tube.
Adding a reaction
reaction gas into
into the
the tube
tube also
also adds
addsadditional
additional occurrences
occurrences of of localised
localised turbulent
turbulent swirls
swirls
of the travelling gas, and, as a result, there is more uncertainty regarding the formation mechanisms
of the particles in the tube. A A fully
fully developed
developed gas gas flow
flow inside
inside the reaction tube yields more uniform
particles. The temperature
temperatureprofile
profilealong
alongthe
thelength
lengthandandcross-section
cross-section of of
thethe
tube tube is related
is related closely
closely to
to the
the
gas gas
flowflow conditions.
conditions. MoreMore
stablestable
flow flow currents
currents againagain
allowallow for a controlled
for a more more controlled temperature
temperature inside
inside
the tubetheand
tube and
less less inconsistency
inconsistency in the particle
in the particle formation.
formation.
Temperature, tube dimensions,
dimensions, gas gas flow, precursor concentration
concentration and ultrasound
ultrasound frequency
frequency
present a complex system of interdependent USP aspects that affect nanoparticle nanoparticle formation.
formation. These
parameters
parameters leaveleave plenty
plenty of manoeuvering
manoeuvering room room for improvements
improvements and and optimisation
optimisation for for a given
particle formation
formation inside
insidethe
theUSP,
USP,although
althoughone one must
must consider
consider whatwhat changes
changes are are introduced
introduced when when
one
one parameter
parameter is altered,
is altered, andand
what what effect
effect this this alteration
alteration has has on the
on the nanoparticle
nanoparticle formation
formation conditions.
conditions.
An
An important
importantelement
elementtotoconsider
considerisisalsoalsothe selection
the selection of of
thethe
precursor
precursor saltsalt
andandits effect on the
its effect on
particle formation.
the particle formation.Most frequently,
Most frequently, metal-containing
metal-containing inorganic
inorganic compounds
compoundsare areused,
used, such
such as
chlorides,
chlorides, nitrates
nitrates and
and sulfates
sulfates [38,52],
[38,52], as
as they
they have
have aa lower
lower volatility
volatility and
and are are more
more prone
prone to form
particles from the Droplet-To-Particle mechanism, discussed in the next chapter. Metal-organic and
organometallic
organometallic compounds
compounds such such asas acetates,
acetates, oxalates,
oxalates, carbonates
carbonates and and alkoxides
alkoxides are are more
more volatile,
volatile,
promoting the Gas-To-Particle conversion mechanism in USP [38,52]. The choice of solvent likewise
facilitates the
the presence
presenceofofliquid
liquidororgasgas phases
phases in the
in the system.
system. TheThe
mostmost
commoncommon solventsolvent is water,
is water, while
while
alcohol,alcohol, ionic liquids
ionic liquids and organics
and organics are usedare used to
in order in modify
order tothe modify thein
volatility volatility
favour ofinthefavour of the
gas particle
gas particle [38].
conversion conversion [38].
Some particles have the tendency to agglomerate in the collection system after synthesis, due to
their high surface energies. For these nanoparticles (in general for all such nanomaterials), it is also
imperative to prevent their agglomeration with the use of suitable collection mediums and stabilisers.
Some particles have the tendency to agglomerate in the collection system after synthesis, due to
Materials
their high 13, 3485 energies.
2020,surface For these nanoparticles (in general for all such nanomaterials), it is7also
of 28
imperative to prevent their agglomeration with the use of suitable collection mediums and stabilisers.
3. Particle Formation with USP
3. Particle Formation with USP
3.1. Droplet-To-Particle Conversion Mechanism in USP
3.1. Droplet-To-Particle Conversion Mechanism in USP
The liquid-to-solid and solid-to-solid conversion processes with USP can be described with the
The liquid-to-solid and solid-to-solid conversion processes with USP can be described with the
DTP mechanism. This mechanism, in general, consists of the formation of droplets, transportation of
DTP mechanism. This mechanism, in general, consists of the formation of droplets, transportation of
these droplets into a heating zone, evaporation of the solvent and thermal conversion of the solute
these droplets into a heating zone, evaporation of the solvent and thermal conversion of the solute
into the final nanoparticles. As the droplet with dissolved material is being evaporated it shrinks,
into the final nanoparticles. As the droplet with dissolved material is being evaporated it shrinks,
and, simultaneously, increases the mass fraction of the solute inside the droplet. The solute can begin
and, simultaneously, increases the mass fraction of the solute inside the droplet. The solute can begin
to precipitate before uniform saturation is reached across the droplet because the solute diffusion is
to precipitate before uniform saturation is reached across the droplet because the solute diffusion is
slower than the evaporation of the solvent. As the solid material is being precipitated on the droplet
slower than the evaporation of the solvent. As the solid material is being precipitated on the droplet
surface due to supersaturation, the liquid can become trapped in the centre. It then begins to evaporate
surface due to supersaturation, the liquid can become trapped in the centre. It then begins to
through the newly formed surface crust (Figure 4). This slows down the evaporation rate.
evaporate through the newly formed surface crust (Figure 4). This slows down the evaporation rate.
Figure 4.
Figure 4. Evaporation
Evaporation of
of aerosol
aerosol droplet
droplet and
and drying
drying of
of the
the precipitated
precipitated solute,
solute, adapted from[53]
adaptedfrom [53]..
Solute precipitation
Solute precipitation in droplets has not been been described
described by by any
anytheory
theoryin inaaquantitative
quantitativemanner.
manner.
For aa given
For given solute,
solute, the
the supersaturation
supersaturation required for precipitation
precipitation must
must bebe measured
measured [4,54],
[4,54], and
and isis aa
function of
function of the
the exact
exact composition
composition of the the solution
solution (impurities act as precipitation sites). Because
Because the
the
rate of
rate of nucleation
nucleation determines particle morphology, the evaporation determines determines particle
particle morphology
morphology
(evaporationdepends
(evaporation dependson on a number
a number of factors,
of factors, such as such as surrounding
surrounding vapour
vapour pressure andpressure and
temperature).
temperature).
Intraparticle reactions, such as thermal decomposition, also occur in the aerosol before and
after Intraparticle reactions, such
solvent evaporation, and ascanthermal decomposition,
influence also occur in the
particle morphology. aerosol
These before
were and after
studied with
solvent evaporation, and can influence particle morphology. These were
thermogravimetric analysis, differential thermal analysis and differential scanning calorimetry [4]. studied with
thermogravimetric
The analysis, differential
precursor characteristics thermal analysis
determine whether hollow or and differential
porous scanning
particles calorimetry
are formed. Whether [4].a
The precursor
precursor meltscharacteristics determine
or not before reacting has awhether hollow
very distinct or porous
difference particles
on the are formed.morphology.
final nanoparticle Whether a
precursor
The volumemelts or of
fraction not
thebefore
solute reacting has a the
also influences very distinct of
formation difference
porous oron the final
hollow nanoparticle
particles, as does a
morphology.
high reductionThe volumebecause
of volume fractionofofreactions,
the solute also in
shown influences
Figure 5.the
An formation
example ofoftheporous or hollow
particles formed
particles,
by the DTP asmechanism
does a highisreduction
shown inofFigure
volume7. because of reactions, shown in Figure 5. An example of
the particles formed by the DTP mechanism is shown in Figure 7.
Materials 2020, 13, 3485 8 of 28
Figure
Figure 5.
5. Types
Types of
of nanoparticles
nanoparticles that
that can
can be
be synthesised
synthesised from
from an
an aerosol
aerosol droplet,
droplet, depending
depending on
on the
the
parameter conditions, adapted from [55]
parameter conditions, adapted from [55]. .
3.2. Gas-To-Particle
3.2. Gas-To-Particle Conversion
Conversion Mechanism
Mechanism in
in USP
USP
The GTP
The GTP formation
formation mechanism
mechanism generally
generally follows
follows thethe supersaturation
supersaturation of of aa gaseous
gaseous species
species ofof the
the
desired material, which causes nucleation and new particle formation.
desired material, which causes nucleation and new particle formation. The particles can be created The particles can be created
by chemical
by chemicalreactions
reactionsof ofgaseous
gaseousprecursors,
precursors,or orby
byphysical
physicalprocesses,
processes,such
suchas ascooling
coolingofofhothotvapour.
vapour.
The average particle diameter, total particle concentration, size distribution
The average particle diameter, total particle concentration, size distribution and particle morphology and particle morphology
evolve along
evolve along the theaerosol
aerosolreactor
reactorin in
twotwo different modes.
different One One
modes. modemodeis nucleation–condensation,
is nucleation–condensation, where
a monomer
where (a gas-phase
a monomer molecule) molecule)
(a gas-phase is formed by is aformed
chemicalbyreaction or a decrease
a chemical reactioninor temperature
a decreaseuntil in
nucleation occurs. The saturation ratio increases, and growth of
temperature until nucleation occurs. The saturation ratio increases, and growth of the the monomer proceeds by condensation
monomer
of the monomer
proceeds onto the particles.
by condensation When no collisions
of the monomer onto the occur,
particles.theyWhen
can remain nearly spherical
no collisions through
occur, they can
the aerosol reactor path. Surface reaction on the particles may also occur,
remain nearly spherical through the aerosol reactor path. Surface reaction on the particles may also promoting growth. Another
mode promoting
occur, is nucleation–coagulation,
growth. Anotherwhere mode is particles are formed and their
nucleation–coagulation, wherehigh concentration
particles are formed allows
and
collisions
their high and coalescenceallows
concentration of particles, resulting
collisions in the growth
and coalescence of of the particles.
particles, Bothinmodes
resulting can be of
the growth found
the
in laboratory processes, while nucleation–condensation is usually not found
particles. Both modes can be found in laboratory processes, while nucleation–condensation is usually in industrial systems.
In theinnucleation–condensation
not found industrial systems. mode, the morphology of the particles depends on collisions and
coalescence. Particles coalesce by sintering
In the nucleation–condensation mode, the after collisions in
morphology oforder to become
the particles spherical.
depends The ratio
on collisions and of
rates of collisions and coalescence (α [4,56,57]) determines the morphology.
coalescence. Particles coalesce by sintering after collisions in order to become spherical. The ratio of
c In collision-limited growth
(αc = of
rates ∞),collisions
the sintering andrate is rapid relative
coalescence to collisions,
(αc [4,56,57]) allowingthe
determines for morphology.
the formation of In spherical particles
collision-limited
between(αcollisions.
growth In sintering-limited growth (αc =collisions,
c = ∞), the sintering rate is rapid relative to
0) the particles
allowingexist
forasthe
aggregates.
formationIntermediate
of spherical
conditions
particles between(α c ≈ 1)collisions. In sintering-limited growth (αc = 0) the particles exist is
are in existence in real situations, where the particle morphology asaaggregates.
function of
parameters that
Intermediate control the
conditions (αc sintering
≈ 1) are inrate—temperature and material
existence in real situations, whereproperties.
the particleThemorphology
primary particleis a
size is also a function of these parameters (Figure 6).
function of parameters that control the sintering rate—temperature and material properties. The
primary When the aerosol
particle size is droplet evaporates
also a function within
of these the GTP mechanism,
parameters (Figure 6). the solute is vapourised along
with the solvent, resulting in the presence of the solute vapours and their partial vapour pressure.
When saturation of vapours is reached, nucleation occurs, and growth of particles proceeds as described
previously. Particles formed by the GTP conversion are typically smaller than the particles formed
by the DTP mechanism. A comparison of the particles formed by these two mechanisms is shown in
Figure 8.
Materials 2020, 13, 3485 9 of 28
Figure 6.
Figure 6. The
The ratios
ratios of
of collisions
collisions and
and coalescence
coalescence with
with the
the Gas-To-Particle (GTP) mechanism
Gas-To-Particle (GTP) mechanism and
and the
the
resulting nanoparticle
resulting nanoparticle morphologies,
morphologies, adapted
adapted from [4,56].
from [4,56].
4. Synthesis
When the ofaerosol
AuNPsdroplet evaporates within the GTP mechanism, the solute is vapourised along
with the solvent, resulting in the presence of the solute vapours and their partial vapour pressure.
4.1. Gold Chloride Precursor
When saturation of vapours is reached, nucleation occurs, and growth of particles proceeds as
Therepreviously.
described are variousParticles
raw materials which
formed can
by the be used
GTP for preparing
conversion precursor
are typically solutions
smaller forparticles
than the AuNPs’
synthesis
formed by(compounds containingAAu:
the DTP mechanism. AuBr3 , HAu(NO
comparison ) , Au(O
of the particles
3 4 CCH
formed
2 )by
3 3 ). In our
these case,
two gold chloride
mechanisms is
or tetrachloroauric
shown in Figure 8.acid HAuCl4 (s) was investigated the most extensively with USP synthesis, due to its
price, availability and chemical stability. The precursor solution was prepared by dissolving HAuCl4
4. Synthesis
in of AuNPs
water [31,46]. It was also confirmed that AuNPs’ synthesis is possible from homemade H-HAuCl4 ,
completed through the chlorine gas method by using HCl and KMnO4 for dissolving a gold pellet in
4.1. Gold
water Chloride Precursor
[58].
By using
There are concentrations of dissolved
various raw materials which Au
can from 0.5for
be used g/Lpreparing
to 5.0 g/Lprecursor
Au in thesolutions
precursorforsolution,
AuNPs’
each droplet contains such an amount of material that, after evaporation and drying,
synthesis (compounds containing Au: AuBr3, HAu(NO3)4, Au(O2CCH3)3). In our case, gold chloride nanoparticles are
formed with diameters from a few 10 nm (at 0.5 g/L Au) up to more than 100 nm (at 5.0
or tetrachloroauric acid HAuCl4(s) was investigated the most extensively with USP synthesis, due to g/L Au in the
precursor solution). and chemical stability. The precursor solution was prepared by dissolving
its price, availability
Droplets
HAuCl4 in waterof the starting
[31,46]. solution
It was are transported
also confirmed into the
that AuNPs’ furnaceiswith
synthesis a carrier
possible fromgas. Inside the
homemade H-
furnace,
HAuCl4, the AuNPs through
completed are formedtheaccording to the
chlorine gas following
method synthesis
by using HCl andstages:
KMnO4 for dissolving a gold
pelletEvaporation
1. in water [58]. and droplet shrinkage (HAuCl4 with water)—above 100 ◦ C;
By using concentrations of dissolved Au from 0.5 g/L to 5.0 g/L Au in the precursor solution,
2. Thermal decomposition of HAuCl4 into AuCl3 —at 258 ◦ C (theoretical);
each droplet contains such an amount of material that, after evaporation and drying, nanoparticles
3. Reduction of AuCl3 with hydrogen gas and the formation of Au—above 300 ◦ C;
are formed with diameters from a few 10 nm (at 0.5 g/L Au) up to more than 100 nm (at 5.0 g/L Au
4. Densification (sintering processes).
in the precursor solution).
Droplets
The listedofsynthesis
the starting solution
stages are transported
are taking into the furnace
place in a disordered fashionwith a carrier
inside the USP gas.
tubeInside the
furnace,
furnace, the AuNPs are formed according to the following synthesis stages:
as different phases of the starting material are present simultaneously at various points in the process.
With the initially smaller
1. Evaporation diameters
and droplet of the
shrinkage aerosol
(HAuCl droplets with diameters ≈1 µm, nanoparticles are
4 with water)—above 100 °C;
formed much sooner than with larger droplets
2. Thermal decomposition of HAuCl4 into AuCl3—at with diameters ≤10 µm. Different droplet sizes are
258 °C (theoretical);
inherent in the aerosol
3. Reduction of AuCldroplet generation, as the nebuliser produces droplets in a size distribution,
3 with hydrogen gas and the formation of Au—above 300 °C;
rather than uniformly sized droplets.
4. Densification (sintering processes). The droplets are also ejected from the solution in a mist, making
collisions between droplets difficult to prevent during gas transportation.
The listed synthesis
Therefore, some solid stages are takinghave
nanoparticles place in a disordered
already formed infashion inside
the reactor thewhile
tube, USP tube
somefurnace,
aerosol
as different phases of the starting material are present simultaneously at various points in the process.
droplets have not yet evaporated at the same point inside the reactor tube. This results in synthesising
With thesizes
various initially smallerand
and regular diameters
irregularofshapes
the aerosol droplets with
of nanoparticles, duediameters ≈1 µm, nanoparticles
to aerosol collisions are
and coagulation.
formed much sooner than with larger droplets
This is not suitable for synthesising more uniform AuNPs.with diameters ≤10 µm. Different droplet sizes are
inherent in the aerosol droplet generation, as the nebuliser produces droplets in a size distribution,
rather than uniformly sized droplets. The droplets are also ejected from the solution in a mist, making
collisions between droplets difficult to prevent during gas transportation.
Materials 2020,Therefore,
13, 3485 some solid nanoparticles have already formed in the reactor tube, while some aerosol 10 of 28
droplets have not yet evaporated at the same point inside the reactor tube. This results in synthesising
various sizes and regular and irregular shapes of nanoparticles, due to aerosol collisions and
With the conventional
coagulation. USP, we
This is not suitable forhave synthesised
synthesising AuNPsAuNPs.
more uniform with sizes ranging from 10 to 300 nm,
With
with different the conventional
shapes, USP, we have
from spherical, synthesised
irregular, AuNPsand
triangular with cylindrical
sizes rangingin
from 10 to 300
a single nm, [46,47].
batch
with different shapes, from spherical, irregular, triangular and cylindrical
Such AuNPs were not suitable for fine-tuning of their properties (Figure 7). in a single batch [46,47].
Such AuNPs were not suitable for fine-tuning of their properties (Figure 7).
Figure 7. TEM images of AuNP shapes and sizes produced in a single batch with the conventional
Figure 7. TEM images of AuNP shapes and sizes produced in a single batch with the conventional
Ultrasonic Spray Pyrolysis (USP).
Ultrasonic Spray Pyrolysis (USP).
In order to alleviate this phenomenon and produce more uniform AuNPs in size and shape, the
In reaction
order to gasalleviate this phenomenon
was introduced at a later stage inand produce
the tube reactormore uniform
(modified AuNPs
USP). This allowsinfor
size and shape,
droplet
the reaction
evaporation and aerosol particle drying before thermal decomposition and reactions take place allows
gas was introduced at a later stage in the tube reactor (modified USP). This for for
final particle formation. In this way, more control could be achieved
droplet evaporation and aerosol particle drying before thermal decomposition and reactions take over the rate of droplet
place forevaporation and the
final particle rate of precursor
formation. In thissalt diffusion
way, moreinside thecould
control droplet. beThese rates with
achieved overUSPthesynthesis
rate of droplet
depend on several factors: precursor solution concentration, droplet sizes, number of droplets and
evaporation and the rate of precursor salt diffusion inside the droplet. These rates with USP synthesis
relative humidity in the system, velocity of droplet transportation inside the furnace, pressure in the
dependsystem,
on several factors:
dimensions precursor
of the transport solution
pipes and concentration,
temperature profiledroplet
inside sizes, number
the furnace. of droplets
For setting up and
relativesuitable
humidity in the system, velocity of droplet transportation inside the furnace,
parameters (precursor solution concentration, gas flow, furnace temperature), information pressure in the
system,isdimensions
needed for the ofstarting
the transport
solution pipes andsuch
properties, temperature profile
as density and surfaceinside theand
tension furnace. For setting up
characteristics
suitableofparameters
the dissolved(precursor
HAuCl4 diffusion
solutioninside the solution and
concentration, gasAuNP
flow,growth.
furnace temperature), information is
needed for the Several experiments
starting solutionwith different parameters
properties, were performed
such as density and surface withtension
the modified USP. The
and characteristics of
synthesised AuNPs were characterised with various characterisation techniques for identification of
the dissolved HAuCl4 diffusion inside the solution and AuNP growth.
their sizes, shapes, chemical composition and degree of agglomeration. Based on these results, we
Several experiments
have surmised withofdifferent
the influence parameters
individual USP parameterswereon theperformed
AuNP formation with the modified
mechanisms. We USP.
The synthesised AuNPs
have identified thatwere characterised
the AuNPs are formed with
fromvarious
dropletscharacterisation
and from the gas techniques for identification
phase. This means that
of theirthey
sizes,
are shapes,
formed from chemical composition
a combination of DTP andandGTPdegree of agglomeration.
formation mechanisms (Figure Based on these
8) [47,59]. Gold results,
we havechloride
surmisedis highly
the hygroscopic,
influence ofacidic and a highly
individual USPvolatile gold salt.
parameters onUsing this salt formation
the AuNP in the USP process
mechanisms.
requires great control over the process, in order to produce AuNPs of the desired shapes and sizes,
We have identified that the AuNPs are formed from droplets and from the gas phase. This means that
due to the mixture of gas and solid phases present in the reaction tube, as well as the inherent physical
they areandformed from a combination of DTP and GTP formation mechanisms (Figure 8) [47,59]. Gold
chemical phenomena that are being performed inside the tube furnace (collisions, coalescence,
chlorideaggregation,
is highly hygroscopic,
agglomeration,acidic
etc.). and a highly volatile gold salt. Using this salt in the USP process
requires great control over the process, in order to produce AuNPs of the desired shapes and sizes, due
to the mixture of gas and solid phases present in the reaction tube, as well as the inherent physical
and chemical phenomena that are being performed inside the tube furnace (collisions, coalescence,
aggregation, agglomeration, etc.).
In order to obtain uniform nanoparticles with such highly volatile precursors, a balancing act is
needed between the physical events of the aerosol, governed by the USP parameters, and the chemistry
of the used formulations. A helpful representation of the effect of these parameters on the particle
growth and morphology is the residence time of the aerosol particles in the reaction furnace, as shown
in Figure 9. Initially, primary particles are formed from the precursor. These particles may then be
joined closely to each other by chemical forces (covalent, ionic), forming necks and hard agglomerates
or aggregates, which are difficult to break apart into primary particles. Soft agglomerates (simply
called agglomerates) are composed of loosely attached primary particles or aggregates by physical
forces (electrostatic, van der Waals), and can be dispersed into individual elements by applying force
or energy (e.g., ultrasound) [10]. The length of each particle growth stage or how long the residence
time of the particles is in each stage of coalescence, aggregation, or agglomeration, determines the final
particle morphology.
have identified that the AuNPs are formed from droplets and from the gas phase. This means that
they are formed from a combination of DTP and GTP formation mechanisms (Figure 8) [47,59]. Gold
chloride2020,
Materials is highly hygroscopic,
13, x FOR PEER REVIEW acidic and a highly volatile gold salt. Using this salt in the USP process
11 of 28
requires great control over the process, in order to produce AuNPs of the desired shapes and sizes,
due to Figure 8. TEM images
the mixture of AuNPs
of gas and produced
solid phases with the
present modified
in the USP,
reaction the smaller
tube, as wellnanoparticles (below
as the inherent physical
Materialsand around
2020, 13, 348510 nm) were formed by the GTP conversion mechanism, while the larger
and chemical phenomena that are being performed inside the tube furnace (collisions, coalescence,AuNPs (below 11 of 28
and above 100 nm) were
aggregation, agglomeration, etc.).formed by the Droplet-To-Particle (DTP) conversion mechanism.
In order to obtain uniform nanoparticles with such highly volatile precursors, a balancing act is
needed between the physical events of the aerosol, governed by the USP parameters, and the
chemistry of the used formulations. A helpful representation of the effect of these parameters on the
particle growth and morphology is the residence time of the aerosol particles in the reaction furnace,
as shown in Figure 9. Initially, primary particles are formed from the precursor. These particles may
then be joined closely to each other by chemical forces (covalent, ionic), forming necks and hard
agglomerates or aggregates, which are difficult to break apart into primary particles. Soft
agglomerates (simply called agglomerates) are composed of loosely attached primary particles or
aggregates by physical forces (electrostatic, van der Waals), and can be dispersed into individual
8. TEM
Figure by
elements images
applying of AuNPs
force produced
or energy with the modified
(e.g., ultrasound) USP,
[10]. The the smaller
length of eachnanoparticles (below
particle growth stage
or and
howaround 10 nm)
long the were formed
residence time by
of the
the GTP conversion
particles is in mechanism,
each stage ofwhile the larger AuNPs
coalescence, (belowor
aggregation,
and above 100determines
agglomeration, nm) were formed by particle
the final the Droplet-To-Particle
morphology. (DTP) conversion mechanism.
Figure
Figure 9. 9.Overview
Overviewofofnanoparticle
nanoparticle growth
growth by
by coagulation
coagulationand
andsintering
sinteringdepending
depending onon
thethe
process
process
residence time, adapted for AuNP growth inside the USP process from the model
residence time, adapted for AuNP growth inside the USP process from the model presented presented in [10] .
in [10].
The red line represents the process temperature, while the blue line represents particle diameter.
The red line represents the process temperature, while the blue line represents particle diameter.
OurOur experimental
experimental work
work on chloride
on gold gold chloride
showedshowed
agreementagreement withprocessing
with aerosol aerosol processing
morphology
morphology
models models
[10]. Having [10]. residence
a high Having atimehighproduced
residencea time produced
mixture a mixture
of primary of primary
small particles, small
with larger
particles, with larger aggregates, along with larger particles and agglomerates in a single
aggregates, along with larger particles and agglomerates in a single batch. Decreasing the residence batch.
Decreasing
time the residence
led to more uniformlytime led tospherical
sized, more uniformly
AuNPs. sized,
Thespherical AuNPs. The
main condition for main condition
producing for
uniform,
producing uniform, unaggregated particles is the length of the aggregation stage. Depending on the
unaggregated particles is the length of the aggregation stage. Depending on the length of the aggregation
length of the aggregation stage, two growth routes are shown in Figure 9. A longer residence time in
stage, two growth routes are shown in Figure 9. A longer residence time in this stage enables sintering
this stage enables sintering at elevated temperatures and the formation of irregularly shaped
at elevated temperatures and the formation of irregularly shaped aggregates. Reducing the length
of this stage—i.e., cooling the primary particles shortly after their formation, produces more fine,
spherical AuNPs.
Materials 2020, 13, 3485 12 of 28

aggregates. Reducing the length of this stage—i.e., cooling the primary particles shortly after their
formation, produces more fine, spherical AuNPs.
AA practicalmodel
practical modelwas
wasdrawn
drawn (Figure
(Figure 10),
10), showing
showing the
the dependence
dependenceofoftwotwoinfluential USP
influential USP
parameters, gold concentration in the precursor solution and gas flow. The gold concentration in the
parameters, gold concentration in the precursor solution and gas flow. The gold concentration in the
precursor solution constrains the gold salt solid and gas phase content in the process. The gas flow
precursor solution constrains the gold salt solid and gas phase content in the process. The gas flow
determines the residence time, the droplet evaporation and particle reactions’ times. Synthesis of
determines the residence time, the droplet evaporation and particle reactions’ times. Synthesis of
targeted spherical AuNPs with a size distribution around 50 nm was achieved with these findings
targeted spherical AuNPs with a size distribution around 50 nm was achieved with these findings [59].
[59].
Figure
Figure 10. 10. Practical
Practical formation
formation model model
of AuNPof AuNP synthesis
synthesis in the modified
in the modified USP. The
USP. The typical typical
morphologies
morphologies are shown using high or low Au concentration in the precursor solution and
are shown using high or low Au concentration in the precursor solution and high or low gas flow high or in
low gas flow in the USP device.
the USP device. Adapted from [59]. Adapted from [59].
4.2.4.2.
Gold Acetate
Gold AcetatePrecursor
Precursor
Solid
Solid phase
phase metalacetate
metal acetateprecursors,
precursors,such
suchas
as Au
Au (III)
(III) acetate, Au(O
Au(O22CCHCCH3)33), have
)3 ), haveshown
shown great
great
potential to expand the composition and structures of nanoparticles. Gold acetate
potential to expand the composition and structures nanoparticles. Gold acetate was always readily was always readily
available,
available, even
even though
though its low
its low solubility
solubility in most
in most solvents
solvents limits
limits its in
its use usetheinsynthesis
the synthesis of AuNPs
of AuNPs [17,60].
[17,60].
The chemistry of this salt and its effects on synthesis mechanisms in the USP were investigated with
several The chemistry trials
experimental of thisfor
saltproducing
and its effects on synthesis
AuNPs. The main mechanisms
byproduct in ofthe
goldUSP weredecomposition
acetate investigated
with several experimental trials for producing AuNPs. The main
is acetic acid [61], which further influences the morphology of the formed AuNPs, showing byproduct of gold acetate
clear
decomposition is acetic acid [61], which further influences the morphology
differences when compared to the AuNP structures formed with gold chloride. Gold acetate was of the formed AuNPs,
showing clear differences when compared to the AuNP structures formed with gold chloride. Gold
selected as an alternative precursor to gold chloride for USP synthesis of AuNPs, with the aim of
acetate was selected as an alternative precursor to gold chloride for USP synthesis of AuNPs, with
obtaining spherical AuNPs with a narrower size distribution and higher concentration.
the aim of obtaining spherical AuNPs with a narrower size distribution and higher concentration.
The results showed a much smaller particle size when compared to gold chloride AuNPs, along
The results showed a much smaller particle size when compared to gold chloride AuNPs, along
with the formation of mesh-like agglomeration structures (Figure 11). This suggests that the addition of
with the formation of mesh-like agglomeration structures (Figure 11). This suggests that the addition
acetic acid in
of acetic theinaerosol
acid flow induces
the aerosol the formation
flow induces mechanisms
the formation to follow
mechanisms a route
to follow of primary
a route particle
of primary
formation and soft orand
particle2020,
formation hard agglomeration
soft of these nanoparticles,
or hard agglomeration depending
of these nanoparticles, on the synthesis
depending conditions.
on the synthesis
Materials 13, x FOR PEER REVIEW 13 of 28
conditions.
Figure
Figure 11.11. STEMimages
STEM imagesofofAuNPs
AuNPs synthesised
synthesised from
from Au
Auacetate
acetatewith
withthe
themodified
modifiedUSP,
USP,showing thethe
showing
formation of a mesh-like structure composed of primary particles.
4.3. Gold Nitrate Precursor

Gold nitrate, HAu(NO3)4, was chosen as an additional precursor for AuNP synthesis with USP,
and for comparison of the produced nanoparticle morphology. Commercially available gold nitrate
is poorly soluble in water, and an investigation was needed for preparing a soluble and chemically
Materials 13, STEM
2020,11.
Figure 3485 images of AuNPs synthesised from Au acetate with the modified USP, showing the
13 of 28

Gold nitrate, HAu(NO ) , was chosen as an additional precursor for AuNP synthesis with USP,
Gold nitrate, HAu(NO33)44, was chosen as an additional precursor for AuNP synthesis with USP,
and for comparison of the produced nanoparticle morphology. Commercially available gold nitrate is
and for comparison of the produced nanoparticle morphology. Commercially available gold nitrate
poorly soluble in water, and an investigation was needed for preparing a soluble and chemically stable
is poorly soluble in water, and an investigation was needed for preparing a soluble and chemically
water-based gold nitrate precursor [34]. The preparation of a precursor solution required reflux boiling
stable water-based gold nitrate precursor [34]. The preparation of a precursor solution required reflux
and additional steps to make it usable within the USP process.
boiling and additional steps to make it usable within the USP process.
The results showed highly spherical AuNPs with a mean size of about 174 nm at a precursor
The results showed highly spherical AuNPs with a mean size of about 174 nm at a precursor
starting concentration
starting concentration ofof2.5
2.5ggof
ofdissolved
dissolvedAuAuper
perlitre.
litre.The
Thenanoparticles
nanoparticleswere
werealso
alsohollow,
hollow,which
whichisisa
structure not obtained with the previously used gold salts.
a structure not obtained with the previously used gold salts.
With the
With thedifferent
differentprecursor
precursorsalts used
salts for AuNP
used for AuNPsynthesis with USP
synthesis withupUSP
to date,
up atogeneral
date, aoverview
general
of the morphologies of the nanoparticles can be given, as shown in Figure 12.
overview of the morphologies of the nanoparticles can be given, as shown in Figure 12.
Figure 12. TEM

Figure 12. TEM overview
overview ofof AuNPs
AuNPs synthesised
synthesised with
with the
the modified
modified USP
USP showing
showing the
the different
different
nanoparticle structures obtained from the precursors used in the experimental investigations.
nanoparticle structures obtained from the precursors used in the experimental investigations.
5. Synthesis
Synthesis of
of Particles Decorated with Nanoparticles
Nanoparticles of
Nanoparticles of different materials have varied properties that make them interesting for
implementation in novel products. Metallic
implementation Metallic nanoparticles
nanoparticles have
have enhanced
enhanced optical
optical properties
properties due to
Surface Plasmon
PlasmonResonance
Resonance (Ag, AuAu
(Ag, [1]),[1]),
while they may
while they also
mayhave
alsoantimicrobial (ZnO [62]),
have antimicrobial magnetic
(ZnO [62]),
(Fe O
magnetic
2 3 [1]), catalytic properties (Ag [63]), or a high electrochemical capacity for electrode
(Fe2O3 [1]), catalytic properties (Ag [63]), or a high electrochemical capacity for electrode materials
(LiFePO
materials 4 -C [64]), able
(LiFePO to be used
4-C [64]), in be
able to biotechnology, magnetic separation
used in biotechnology, magneticprocesses,
separationsensors or electronic
processes, sensors
and
or energy devices.
electronic and energyBy combining
devices. Bytwo differenttwo
combining nanomaterials, it is possible to
different nanomaterials, combine
it is possibleand improve
to combine
theirimprove
and characteristics and increase their
their characteristics andpotential
increase application. One
their potential of the mostOne
application. commonof theways
mosttocommon
achieve
this isto
ways byachieve
using binary
this is systems.
by using binary systems.
Bimetallic particles are functional materials for applications, produced by joining two elements
in some type of construction, such as core–shell, alloy or otherwise [65,66]. The combined features
of the two materials can result in new effects and properties, or improve existing ones, such as
enhanced catalysis or tunable plasmonic properties. These composite structures may be used for
various novel applications in catalytic processes [65], sensor devices [65], Electronics, for Magnetic
Resonance Imaging [67–69], photothermal treatment of cancer [70] and drug delivery systems [67–69].
The flexibility of the USP process allows it to be used for the production of such composite
particles by dissolving several precursor salts in the starting solution. It is also possible to use several
in some type of construction, such as core–shell, alloy or otherwise [65,66]. The combined features of
the two materials can result in new effects and properties, or improve existing ones, such as enhanced
catalysis or tunable plasmonic properties. These composite structures may be used for various novel
applications in catalytic processes [65], sensor devices [65], Electronics, for Magnetic Resonance
Imaging2020,
Materials [67–69], photothermal treatment of cancer [70] and drug delivery systems [67–69]. 14 of 28
13, 3485
The flexibility of the USP process allows it to be used for the production of such composite
particles by dissolving several precursor salts in the starting solution. It is also possible to use several
ultrasonic
ultrasonic generators,
generators, and
and introduce
introduce the
the produced
produced aerosol
aerosol into
into the
the same
same material
material flow.
flow. As
As such,
such, we
we
have used USP to produce complex Ag/TiO , Au/TiO and Au/Fe O nanoparticles.
have used USP to produce complex Ag/TiO22, Au/TiO22 and Au/Fe22O3 nanoparticles.
5.1. Ag/TiO22 and

5.1. Ag/TiO and Au/TiO
Au/TiO22 Nanoparticles
Nanoparticles
The
The produced
produced metal/oxide
metal/oxideAg/TiOAg/TiO 2 2and
andAu/TiO
Au/TiO 2 2nanoparticles
nanoparticleswere were produced
produced byby USPUSPforfor
useuse
in
photocatalytic applications. The catalytic properties of the Ag and Au nanoparticles
in photocatalytic applications. The catalytic properties of the Ag and Au nanoparticles are enhanced are enhanced by
the
by oxide
the oxide substrate. The demands
substrate. The demandsfor optimalfor catalytic
optimal properties are small noble
catalytic properties metal nanoparticle
are small noble metal
size
nanoparticle size and low content of noble metal in the shell (up to a maximum of2 was
and low content of noble metal in the shell (up to a maximum of 10%) [38]. TiO 10%)selected
[38]. TiO as2
the
wasAg and AuNP
selected as thesubstrate
Ag and AuNPor coresubstrate
material or due to its
core inertness,
material duechemical stability,
to its inertness, nontoxicity
chemical [71]
stability,
and antimicrobial properties [72,73].
nontoxicity [71] and antimicrobial properties [72,73].
The
The selected
selected precursor
precursor for forTiO
TiO22particle
particleformation
formationwas wastetra-n-butylorthotitanate,
tetra-n-butylorthotitanate,CC1616H H3636O Ti,
O44Ti,
while
while gold
gold chloride,
chloride, HAuCl
HAuCl44 and and silver
silver nitrate,
nitrate, AgNO
AgNO3,3, werewere used
used forfor synthesis
synthesis of of the
the Au
Au and
and Ag Ag
particles.
particles. The titanium-containing compound C16H36O4Ti was first stabilised with hydrochloric acid
The titanium-containing compound C 16 H 36 O 4 Ti was first stabilised with hydrochloric acid
or
or nitric
nitric acid
acid for
for the
the precursor
precursor solution
solution preparation,
preparation, as as it
it hydrolyses
hydrolyses andand decomposes
decomposes in in contact
contact with
with
water.
water. Gold chloride or silver nitrate were added into the prepared titanium precursor solution in
Gold chloride or silver nitrate were added into the prepared titanium precursor solution in
various
various concentration
concentrationratios. ratios.TheThefinal prepared
final solution
prepared was then
solution was used
then in the USP
used process
in the USP for Ag/TiO
process for2
and
Ag/TiOAu/TiO
2 and
nanoparticle
2 Au/TiO synthesis at temperatures up to 1000 ◦ C [36].
2 nanoparticle synthesis at temperatures up to 1000 °C [36].
Figure ◦ C.
Figure 13 13 shows
shows examples
examples of of the
the Ag/TiO nanoparticles obtained
Ag/TiO22 nanoparticles obtained withwith USP
USP at at 800
800 and
and 1000
1000 °C.
Irregular
Irregular morphologies
morphologies of of the
the oxide
oxide particles
particles are
are visible,
visible, with
with the
the oxide
oxide particles
particles being
being covered
covered withwith
Ag
Ag nanoparticles. The distribution of the Ag nanoparticles on the surface areas of the oxide is not
nanoparticles. The distribution of the Ag nanoparticles on the surface areas of the oxide is not
homogeneous
homogeneous when when aa lower
lower Ag Ag concentration
concentration is is used
used in in the
the precursor
precursor solution.
solution. When
When aa higher
higher Ag Ag
concentration
concentration is is used
used inin the
the precursor
precursor solution,
solution, thethe coverage
coverage of of Ag
Ag nanoparticles
nanoparticles on on top
top of
of oxide
oxide
particles
particles is is more
moreuniform.
uniform.This Thiswaswas also
also thethe
casecase
when when higher
higher synthesis
synthesis temperatures
temperatures were were used
used (1000
(1000 ◦ C). The increase in temperature is believed to have a positive influence on the particle formation
°C). The increase in temperature is believed to have a positive influence on the particle formation
kinetics
kinetics andand precursor
precursor saltsalt diffusion
diffusion inside
inside the
the aerosol
aerosol droplet,
droplet, since
since it
it facilitates
facilitates the
the Ag
Ag nanoparticle
nanoparticle
distribution
distribution on the oxide surface. Higher Ag concentrations and higher temperatures also
on the oxide surface. Higher Ag concentrations and higher temperatures also cause
cause thethe
Ag
Ag nanoparticles to be formed in more irregular shapes as compared to other experiments, where the
nanoparticles to be formed in more irregular shapes as compared to other experiments, where the
spherical shape of these nanoparticles
spherical shape of these nanoparticles was present. was present.
Figure 13. SEM images of the produced Ag/TiO2 nanoparticles, adapted from [36], (a) Ag content
20 wt.% with a reaction temperature of 800 ◦ C, (b) Ag content 40 wt.% with a reaction temperature of
800 ◦ C, (c) Ag content 40 wt.% with a reaction temperature of 1000 ◦ C.
The produced TiO2 particles had a spherical solid shape with sizes ranging from 200 to 300 nm.
The Ag nanoparticles were mostly spherical with an average size of around 50 nm [36,37].
Figure 14 shows examples of the Au/TiO2 nanoparticles obtained with USP at 550, 800 and 1000 ◦ C.
The core TiO2 particle sizes were similar in all of the experiments, while the AuNPs formed in irregular,
wt.% with a reaction temperature of 800 °C, b) Ag content 40 wt.% with a reaction temperature of 800
°C, c) Ag content 40 wt.% with a reaction temperature of 1000 °C.
The produced TiO2 particles had a spherical solid shape with sizes ranging from 200 to 300 nm.
The Ag 2020,
Materials nanoparticles
13, 3485 were mostly spherical with an average size of around 50 nm [36,37]. 15 of 28
Figure 14 shows examples of the Au/TiO2 nanoparticles obtained with USP at 550, 800 and 1000
°C. The core TiO2 particle sizes were similar in all of the experiments, while the AuNPs formed in
spherical cubic and triangular shapes, in sizes around 10 nm. The main distinction is the AuNP
irregular, spherical cubic and triangular shapes, in sizes around 10 nm. The main distinction is the
coverage on the core TiO2 particles.
AuNP coverage on the core TiO2 particles.
Figure 14. SEM images of the produced Au/TiO2 nanoparticles, adapted from [36], a) reaction
Figure 14. SEM images of the produced Au/TiO2 nanoparticles, adapted from [36], (a) reaction
temperature of 550 ◦°C, b) reaction temperature of 800 °C, c) reaction temperature of 1000 °C.
temperature of 550 C, (b) reaction temperature of 800 ◦ C, (c) reaction temperature of 1000 ◦ C.
Focus
Focus Ion
Ion Beam
Beam(FIB)
(FIB)milling
millingshowed
showedthe
thepresence
presenceofof
AuNPs
AuNPs inside thethe
inside TiOTiO
2 particles, while, for
2 particles, while,
Ag,
for Ag, this was not the case. About 30% of AuNPs were distributed randomly inside the
this was not the case. About 30% of AuNPs were distributed randomly inside the TiO
TiO22 particle
particle
volume. More than 90% of Ag particles were distributed on the surfaces of the TiO 2 particles [37].
volume. More than 90% of Ag particles were distributed on the surfaces of the TiO particles [37]. 2
5.1.1. Metal
Metal Nanoparticle
Nanoparticle Nucleation on Oxide Particles
In order to have control
control over the the final
final microstructure,
microstructure, it is important
important to understand
understand the formation
formation
mechanism of these complex nanoparticles, which is led by nucleation nucleation and growth growth [39].
[39]. TiO22 is a
crystalline material
material with three polymorphic phases, namely anatase (tetragonal), (tetragonal), rutile (tetragonal)
(tetragonal)
and brookite
brookite(orthorhombic).
(orthorhombic).DifferentDifferentpolymorphs
polymorphs present different
present nucleation
different sites for
nucleation noble
sites formetals
noble
[74–76].
metals [74–76].
It was found that nucleation of metal nanoclusters initiated at surface defects, which is
thermodynamically
thermodynamically favourablefavourabledue due to to
thethe
highhigh adsorption
adsorption energy energy
and Tiand Ti sites
cation cation sites between
between bridging
bridging
oxygen rows oxygen[75].rows [75]. The
The most stablemost stable
surface forsurface
rutile isfor rutile is as
suggested suggested as (1
(1 1 0) [74], 1 0)for
while [74], whileitfor
anatase is
anatase
identifiedit as
is (1
identified
0 1) [76]. as (1 0 1)and
Defects [76]. Defects
oxygen and oxygen
deficiencies in thedeficiencies in the TiO
TiO2 crystallinity crystallinity
also2play also
an important
play annucleation
role as importantsites role as
fornucleation
the growthsites for the
of noble growth
metal of noble metal
nanoparticles nanoparticles
or clusters. or clusters.
The equilibrium The
shape
equilibrium
of a cluster isshape of a cluster
determined by theisbalance
determinedof theby the balance
forces betweenof thethe forces the
surface, between the surface,
interfacial the
energy and
interfacial
wetting energy and
behaviour wetting
of the clusterbehaviour
[37]. of the cluster [37].
Different metals have different interactions interactions with the the TiO
TiO22 surface, resulting in various
microstructures of the clusters,clusters, depending
depending on on the
the metal
metal type.
type. The surface and crystallographic
crystallographic
properties
properties of the TiO core
2 core
2 particle in relationship
relationship with the noble metal nanoparticles
metal nanoparticles and the interface
between the the two
twocomponents
componentsare areimportant
important considerations
considerations forfor
thethefinalfinal core–shell
core–shell microstructure
microstructure [37].
[37].
5.1.2. Metal/Oxide Nanoparticles’ Formation Model
The noble metal/oxide particle formation with USP follows the same synthesis stage principles as
when using a single precursor [18,19]. As the two components in the aerosol droplets are different in
composition, they begin to diverge in the time frames of when the USP process stages of evaporation,
drying and decomposition occur. Assuming that the two components have minimal influence on
the synthesis stages of each other, a new formation model was proposed for synthesising core–shell
and achieving a critical supersaturation concentration for nucleation.
The change in saturation concentration and position of metals and oxides in the dynamically-
changing droplet/particle volume was proposed as a function of reaction time [37]. The different
reaction times in the model are labelled as t0, t’, t’’, t’’’, where t0 < t’ < t’’ < t’’’. The reaction times have
corresponding droplet/particle radiuses R, R’, R’’, R’’’. Ccrit m is the critical supersaturating
Materials 2020, 13, 3485 16 of 28
concentration of the metallic precursor; Cs m is the saturation concentration of the metallic precursor;
Cs ox is the saturation concentration of the oxide precursor; C m, C’ m, C’’ m and C’’’ m are
concentrationsThe
nanoparticles. of the metallic
model precursor
in Figure at theironcorresponding
15 is based times
solute diffusion and
to the radiuses.
droplet C ox,
surface C’ achieving
and ox, C’’ ox
aand C’’’ ox
critical are concentrations
supersaturation of the oxide
concentration for precursor
nucleation.at their corresponding times and radiuses.
Figure 15. Metal/oxide nanoparticles’ formation model, adapted from [37].
The
As thechange
processin saturation
advances, concentration radius
the droplet/particle and position
decreasesof from metals
R to R’’’.andThe oxides in the
concentration
dynamically-changing
profiles inside the aerosol droplet/particle are shown under the aerosol in Figure 15. Initially,[37].
droplet/particle volume was proposed as a function of reaction time we
The different
assumed reaction times
a homogeneous in the model
concentration are labelled
distribution of theastwo t0,precursor , where t0 <throughout
t0 , t00 , t000components t0 < t00 < the t000 .
The reaction
droplet. The times
droplet have corresponding
begins to evaporatedroplet/particle radiuses R,at
at elevated temperatures R0the, R00given
, R000 . time
Ccritt’,mdecreasing
is the criticalits
supersaturating
diameter and increasingconcentration of the metallicofprecursor;
the concentration Cs m is the
the components at thesaturation
dropletconcentration
surface. The of the
oxide
metallic
precursorprecursor; Cs ox
concentration is the its
reaches saturation concentration of
critical supersaturation the ox)
(Ccrit oxide precursor;
earlier m, C0precursor,
than theCmetal m, C00 m
and 000
C ammuch are concentrations of the metallic precursor at The
theirprecipitation
corresponding times and radiuses.
as it has higher initial concentration in the solution. of the oxide component
C 0
ox, Cfirstly 00
ox, Con ox 000
starts theand C ox
droplet are concentrations
surface. of the oxideofprecursor
Since the concentration the metalatprecursor
their corresponding
had not reachedtimes
and radiuses.
the critical supersaturated concentration yet, the metal component diffused with the solvent to the
As surface
droplet the process advances,
without the droplet/particle radius decreases from R to R000 . The concentration
any precipitation.
profilesAsinside the aerosol
the synthesis droplet/particle
progressed furtherareto shown
reactionunder
timethet’’,aerosol in Figure
the radius 15. Initially,
decreased wethe
further, assumed
oxide
aprecipitation
homogeneous concentration distribution of the two precursor components
moved through the centre of the droplet, and the metal precursor reached the critical throughout the droplet.
The droplet begins
supersaturating to evaporate(Ccrit
concentration at elevated
m). The temperatures at the given
metal precursor is now time t0 , decreasing
precipitating on its
thediameter
droplet
and increasing
surface. the concentration
As identified of the components
earlier, the precipitation at the droplet
and nanoparticle growth surface.
favoursThe oxidewith
surfaces precursor
lower
concentration reaches its critical supersaturation
effective surface energy, such as the grain boundary, defects, etc.(Ccrit ox) earlier than the metal precursor, as it has
a much In higher
the lastinitial
timeconcentration
frame at point in the solution.
t’’’, almost Theall precipitation
of the solvent of the
hadoxide component
evaporated, andstarts
the
firstly on the droplet surface. Since the concentration of the metal precursor
droplet/particle had reached its smallest radius R’’’. In an ideal case, all metallic precursors had had not reached the critical
supersaturated concentration yet, the metal component diffused with the solvent to the droplet surface
without any precipitation.
As the synthesis progressed further to reaction time t00 , the radius decreased further, the oxide
precipitation moved through the centre of the droplet, and the metal precursor reached the critical
supersaturating concentration (Ccrit m). The metal precursor is now precipitating on the droplet
surface. As identified earlier, the precipitation and nanoparticle growth favours surfaces with lower
effective surface energy, such as the grain boundary, defects, etc.
In the last time frame at point t000 , almost all of the solvent had evaporated, and the droplet/particle
had reached its smallest radius R000 . In an ideal case, all metallic precursors had succeeded in diffusing
with the solvent to the droplet/particle surface and precipitated there. In the case that the precipitation
front was moving faster than the diffusion front, some of the metal precipitation may also occur in the
particle volume. This may occur at the relatively low value of Ccrit m, or, in the case of very small
droplets, due to solvent evaporation in the droplet/particle volume [37].
Materials 2020, 13, 3485 17 of 28
In the proposed model, the critical supersaturation concentration defines at which point
the precipitation of the individual component is going to take place. This critical concentration
depends upon the solubility and the molar ratio of the precursor component in the aerosol droplet.
Changing these values gives options for influencing the final metal/oxide core–shell particle formation.
As solubility is determined by the chemistry and composition of the individual precursor components,
this leaves the molar ratio as the determining factor able to be fine-tuned with USP. To achieve the
target metal/oxide morphology, the concentration of the metal precursor should be lower than the
concentration of the oxide precursor in the starting solution. This causes the oxide to precipitate
earlier than the metal and form a substrate for the metal particles. After this precipitation, the usual
synthesis stages of USP take place (completion of evaporation, decomposition/reaction, densification).
This arrangement proposes that the concentration ratios of the two components govern whether a
core–shell microstructure is formed, or whether the core particle becomes decorated with smaller
nanoparticles. The importance of optimal concentration ratios for producing core–shell structures is
also demonstrated with the synthesis of such structures of Ag/Si [77].
5.1.3. Ag/TiO2 and Au/TiO2 Nanoparticles’ Formation Model

For the case of Ag and Au nanoparticles on TiO2 , the differences in solubility of gold chloride and
silver nitrate support the formation of the experimentally obtained final particle structures with this
model. Following the proposed model, the precipitation of the gold chloride or silver nitrate starts when
the critical supersaturation concentration is reached. As Ccrit_AuCl3 < Ccrit_AgNO3 , the precipitation
of gold chloride begins before silver nitrate at the given droplet diameter R00 AuCl3 > R00 AgNO3 .
The formation of the first metal clusters and the growth of noble metal occur on the droplet surface.
As the oxide begins to form, the metal particles develop on the sites with high adsorption energy, which
act as nucleation sites. After this, the precipitation line moves towards the centre of the droplet, and the
diffusion of the precursor continues from the droplet centre towards the surface. As the precipitation
of gold and silver follow the relation R00 AuCl3 > R00 AgNO3 , the diffusion path for gold is longer and
slower, until the radius reaches R000 [37]. The result of the shorter path of silver is seen as less dispersion
of this material across the oxide particle compared to gold, as silver has better conditions for reaching
the droplet/particle surface before precipitating. This is also confirmed by the FIB milling analysis,
showing less Ag nanoparticles in the TiO2 particle volume when compared to Au [36].
These results show that solubility is an important condition for phase separation when such
particles are formed within the USP process. Figures 13 and 14 show the morphological differences
between the Ag/TiO2 and Au/TiO2 nanoparticles—the AuNPs are much finer than AgNPs, and are
also distributed inside the volume of TiO2 . The Ag nitrate precursor also has a melting point of 444 ◦ C,
lower than its temperature of decomposition, causing the AgNPs to grow on top of the oxide particles
in melt form [37]. This also increases coagulation of these particles, resulting in larger AgNP size when
compared to the AuNP sizes.
5.2. Au/Fe2 O3 Nanoparticles

AuNPs have good potential for various applications, due to their properties such as Surface
Plasmon Resonance and high biocompatibility. Adding ferromagnetism as an additional property to
these nanoparticles enhances their applicability and use cases in medical treatment [78,79], for Magnetic
Resonance Imaging [80], cancer treatment [81], drug delivery systems, as well as for catalysis, sensors,
and so on [82–85]. Some initial experiments for determining the capability of producing such particles
with USP were conducted, in order to investigate the formation mechanisms of these particles [86,87].
Different salt combinations containing Fe and Au were used for the USP starting solutions,
in order to investigate the different formation mechanisms. The iron-containing salts were iron
acetate, iron chloride and iron nitrate. Gold acetate, gold chloride and gold nitrate were used for the
gold component. It is not possible to mix these salts in any given combination, as some react with
one another in an aqueous solution, making this solution unusable in USP [86]. It was discovered
Different salt combinations containing Fe and Au were used for the USP starting solutions, in
order to investigate the different formation mechanisms. The iron-containing salts were iron acetate,
iron chloride
Materials 2020, 13,and
3485iron nitrate. Gold acetate, gold chloride and gold nitrate were used for the18gold of 28
component. It is not possible to mix these salts in any given combination, as some react with one
another in an aqueous solution, making this solution unusable in USP [86]. It was discovered that
that using
using different
different combinations
combinations of precursor
of precursor salts produces
salts produces particle
particle shapesshapes that correspond
that correspond to the
to the given
given salt. The iron chloride–gold chloride precursor was proven to be the
salt. The iron chloride–gold chloride precursor was proven to be the most favourable for USP, most favourable for USP,
producing spherical
producing spherical oxide
oxide particles,
particles, decorated
decorated with spherical and
with spherical irregular metal
and irregular metal particles. Other salt
particles. Other salt
combinations produced irregular particles of the oxide, with irregular particles
combinations produced irregular particles of the oxide, with irregular particles of the noble metal. of the noble metal.
Controlling the
Controlling the formation
formation of of these
these particles
particles would
would bebe difficult,
difficult, so
so only
only the
the chloride-chloride
chloride-chloride solution
solution
was pursued
was pursuedfurther
furtherfor forobtaining
obtainingFe Fe
oxide particles
oxide withwith
particles uniformly dispersed
uniformly AuNPsAuNPs
dispersed on theiron surface.
their
The USP synthesis yielded mostly
surface. The USP synthesis yielded mostly Au/Fe O and
2 Au/Fe
3 Au/Fe
2O3 and
O nanoparticles,
3 Au/Fe
4 as the result of the initially
3O4 nanoparticles, as the result of the
chosen USP
initially chosenparameters. Using different
USP parameters. parameters
Using different and temperatures
parameters for changing
and temperatures the iron
for changing theoxide
iron
form into a singular Fe O during synthesis achieved the magnetism characteristics
oxide form into a singular Fe3O4 during synthesis achieved the magnetism characteristics of the
3 4 of the particles,
due to thedue
particles, different
to theformation kinetics. This
different formation may be
kinetics. a subject
This may befora future
subjectendeavours with USP forwith
for future endeavours the
production
USP for the of these particles.
production of these particles.
In order to obtain nanoparticles
In order to obtain nanoparticles with with USP,
USP, the
the overall
overall precursor
precursor concentration should be
concentration should be kept
kept
low, around 1–2 g/L [59,60,86]. Within this constraint, we have used iron chloride
low, around 1–2 g/L [59,60,86]. Within this constraint, we have used iron chloride and gold chloride and gold chloride in
different
in differentconcentration
concentration ratios, ranging
ratios, rangingfrom Fe/Au
from Fe/Au= 0.1 to to
= 0.1 Fe/Au
Fe/Au= 4, as as
= 4, seen
seenin in
Figure
Figure16.16.
Figure 16. Comparison

Figure 16. Comparison of of the
the Au/Fe
Au/Fe22OO33 nanoparticles’
nanoparticles’ structures,
structures, synthesised
synthesised with
with aa precursor
precursor
concentration
concentration ratio ranging from Fe/Au = 0.1 to Fe/Au = 4, adapted from [87]. The white particles
ratio ranging from Fe/Au = 0.1 to Fe/Au = 4, adapted from [87]. The white particles
represent
represent AuNPs,
AuNPs, the
the grey particles are
grey particles Fe2O
are Fe O3.
2 3.
A distinct
distinct particle
particle morphology
morphology and AuNP arrangement
arrangement difference is seen from the images of the
prepared particles. When When usingusing aa low
low concentration
concentration of of iron
iron in
in the precursor solution, the resulting
particles have a greater number of larger AuNPs, which are more heavily agglomerated. As the ratio
increases in favour
favour ofof Fe,
Fe, the
theAuNPs
AuNPsretain
retaingreater
greaternumbers,
numbers,but butbecome
becomesmaller
smaller and
and more
more uniform
uniform in
in shape
shape [87].
[87].
A low
low ratio
ratio of
of Fe/Au
Fe/Au 0.1 showed
showed Fe oxide
oxide particles
particles covered with larger clusters of AuNPs. When When
we increased
increasedthe the Fe/Au ratio to 0.25, lesser agglomeration of the AuNPs was visible,
Fe/Au ratio to 0.25, lesser agglomeration of the AuNPs was visible, but the synthesised but the
synthesised
AuNPs wereAuNPs were when
larger than largerusing
than when using
the lower the lower
Fe/Au ratio.Fe/Au
In theratio. In the experiment
experiment Fe/Au 2, theFe/Au
AuNPs 2,
the AuNPs
became finerbecame
and morefiner and more
evenly evenlyon
distributed distributed on particles,
the Fe oxide the Fe oxide particles,
while whilea large
still having still having
number a
large numbershapes
of irregular of irregular
and someshapes and some agglomeration.
agglomeration. With the Fe/Au With the of
ratio Fe/Au
four,ratio of four, the
the surfaces surfaces
of Fe oxide
of Fe oxide
particles were particles were
decorated withdecorated with more
more uniformly uniformly
dispersed dispersed
finely finelywith
sized AuNPs, sized AuNPs, with
a measured mean a
measured
nanoparticle meansizenanoparticle
of 26 nm. size of 26 nm.
A comparison of the the different
different particle morphologies obtained from the experiments is shown in
Figure 17.
The observations from these experiments show that merely increasing Au content as compared to
Fe content in the droplets does not produce more intrinsically uniform Au coatings, as was assumed
previously. Following the previous metal/oxide formation model, the AuNPs are formed near the
droplet surface, while the Fe oxide particles are formed inside the droplet core, due to the different
solubilities and critical supersaturation conditions of the two components. As the droplet evaporates
and shrinks, the surface chemistry of the system causes the AuNPs near the droplet surface to be
deposited on the Fe oxide particles inside the core of the droplet. Some cases of Fe/Au core–shell
Materials 2020, 13, 3485 19 of 28
synthesis report growth of Au on the Fe core, or growth of Fe on an Au shell, depending on the solvent
type in which the growth took place, whether it was organic, water or otherwise [88–90]. The selection
of solvent for the precursor preparation for USP synthesis may also be revised for continuous Au shell
production [87].
Figure 17. Schematic interpretation of the different Au/Fe2O3 nanoparticle morphologies obtained by
Figure 17. Schematic interpretation of the different Au/Fe2 O3 nanoparticle morphologies obtained by
using different Fe/Au concentration ratios with USP, adapted from [87].
using different Fe/Au concentration ratios with USP, adapted from [87].
The observations
For the Au/Fe2 O3 from
system,these
the experiments showgaps
broad miscibility thatbetween
merely increasing
Fe and Au Au content
results as compared
in complete phase
to Fe content in the droplets does not produce more intrinsically uniform Au
separation [89], while the adhesive forces between the Fe and AuNPs are much lower than the cohesive coatings, as was
assumed previously. Following the previous metal/oxide formation model, the
forces in the AuNPs. This results in the described Au/Fe2 O3 particle morphologies observed in the AuNPs are formed
near the droplet
investigation. Thesurface,
findingwhile the Fe
proposes oxide
that particles are
a continuous formed
layer of Au inside
on topthe droplet
of Fe oxide core, due would
particles to the
different solubilities and critical supersaturation conditions of the two components.
not be possible to achieve with USP, without modifying the adhesive forces between the Fe oxide As the droplet
evaporates
particles andand Aushrinks,
[87]. the surface chemistry of the system causes the AuNPs near the droplet
surface to be
There aredeposited on the Fe
also possibilities oxidean
of using particles inside layer
intermediate the core of thethe
between droplet. Some
metal and casesmade
oxide, of Fe/Au
with
core–shell synthesis report growth of Au on the Fe core, or growth of Fe on an Au shell,
functional groups (citrates, thiols, amines, etc.), enabling the continuous Au shell growth [78,83,85,91]. depending
on the solvent type in which the growth took place, whether it was organic, water or otherwise [88–
6. Synthesis
90]. of Photoluminescent
The selection of solvent for theNanoparticles
precursor preparation for USP synthesis may also be revised for
continuous Au shell production [87].
The need for phosphors, which absorb invisible light and emit visible light, becomes recognisable.
For the Au/Fe2O3 system, the broad miscibility gaps between Fe and Au results in complete
Therefore, techniques including security inks or markers could be transported into wide applications,
phase separation [89], while the adhesive forces between the Fe and AuNPs are much lower than the
such as currency, food security, credit cards, passports, etc. [92,93]. Synthesis of appropriate inks,
cohesive forces in the AuNPs. This results in the described Au/Fe2O3 particle morphologies observed
including a fluorescent component that could be activated with an ultraviolet or visible light, enables
in the investigation. The finding proposes that a continuous layer of Au on top of Fe oxide particles
straightforward detection [94]. The type of phosphor materials is basically composed of a host matrix
would not be possible to achieve with USP, without modifying the adhesive forces between the Fe
with intentionally doped impurities with enhanced light interaction [95,96]. Depending on the radiative
oxide particles and Au [87].
emission mechanisms, photoluminescence can be categorised into two main groups; downconversion
There are also possibilities of using an intermediate layer between the metal and oxide, made
and upconversion, respectively. The former is the conversion of one high energy photon into two
with functional groups (citrates, thiols, amines, etc.), enabling the continuous Au shell growth
lower-energy photons, where the latter occurs through the conversion of multiple photons with lower
[78,83,85,91].
energy into one high energy photon by Near-Infrared Light (NIR) excitation [97]. A host matrix should
be thermally and chemically stable, optically transparent, and should not exhibit big size mismatch
6. Synthesis of Photoluminescent Nanoparticles
with a dopant ion. In order to fulfil these criteria, various materials have been examined by previous
The need
researchers for matrices,
as host phosphors, such which absorb
as: metal rareinvisible light oxysulfides,
earth oxides, and emit visible light,
fluorides, becomes
phosphates,
recognisable.
vanadate [98]. Therefore,
Specifically,techniques
the excellentincluding security inks
optical properties of Y2or
O3,markers couldrefractive
such as high be transported into
index (>1.9),
wide
broadapplications,
transparencysuch rangeas(0.2–8
currency,
µm) food security,
and high light credit
output, cards,
makespassports, etc. [92,93].candidate
it an indispensable Synthesisfor
of
appropriate inks, including a fluorescent component that could be activated with an ultraviolet or
visible light, enables straightforward detection [94]. The type of phosphor materials is basically
composed of a host matrix with intentionally doped impurities with enhanced light interaction
[95,96]. Depending on the radiative emission mechanisms, photoluminescence can be categorised
into two main groups; downconversion and upconversion, respectively. The former is the conversion
criteria, various materials have been examined by previous researchers as host matrices, such as:
metal rare earth oxides, oxysulfides, fluorides, phosphates, vanadate [98]. Specifically, the excellent
optical properties of Y2O3, such as high refractive index (>1.9), broad transparency range (0.2–8 µm)
and high light output, makes it an indispensable candidate for the luminescence applications [99].
Materials 2020, 13, 3485 20 of 28
For the surface plasmon enhancement, noble metal nanoparticles have been utilised, owing to their
strong light absorption, originating from their surface plasmon’s interaction with the light. Surface
the luminescence
plasmons applications
are the oscillating [99]. propagating
waves For the surfacealong
plasmon theenhancement,
surface of the noble metal
metal nanoparticles
owing to electron
have been utilised, owing to their strong light absorption, originating from their surface plasmon’s
clouds, and they produce an intense electromagnetic field. Coupling of the electromagnetic field
interaction with the light. Surface plasmons are the oscillating waves propagating along the surface of
created by plasmons and incident light can improve luminescence properties [100]. An alternative
the metal owing to electron clouds, and they produce an intense electromagnetic field. Coupling of the
strategy is the surface plasmon enhancement of luminescence by incorporating metallic nanoparticles
electromagnetic field created by plasmons and incident light can improve luminescence properties [100].
into An
phosphor
alternative materials.
strategy isThere haveplasmon
the surface been many studies
enhancement conducted on
of luminescence Eu complexmetallic
by incorporating solutions,
including silver, and
nanoparticles the effects
into phosphor of Ag nanoparticles
materials. There have been onmany
photoluminescent
studies conducted (PL)
on efficiency
Eu complexwere
investigated [101–105], even through USP [106]. In this research, it was shown
solutions, including silver, and the effects of Ag nanoparticles on photoluminescent (PL) efficiency that Ag/(Y 0.95 Eu0.05 )2O3
nanocomposite
were investigatedcan be[101–105],
synthesised evenby singleUSP
through USP[106].
at 800In°C temperature
this research, it was andshown
1.5 L/min air flow.
that Ag/(Y 0.95 For
Eu ) O nanocomposite can be synthesised by single USP at 800 ◦ C temperature and 1.5 L/min
this purpose,
0.05 2 3Yttrium nitrate (Y(NO3)3.6H2O), europium nitrate (Eu(NO3)3∙5H2O) and silver nitrate
(AgNOair 3flow.
) were Forused
this purpose, Yttrium of
for preparation nitrate (Y(NO3 )3 .6HDeionised
the precursors. 2 O), europium waternitrate
was(Eu(NO
used as 3 )3 ·5H O) and for
the2solvent
silver nitrate (AgNO
all solutions. In USP synthesis, 3 ) were used for preparation of the precursors. Deionised water
the precursor solutions were prepared by dissolving the relative was used as
the solvent for all solutions. In USP synthesis, the precursor solutions were prepared by dissolving
amounts of Y(NO3)3.6H2O, Eu(NO3)3∙5H2O and AgNO3. The USP process starts with melting of the Y
the relative amounts of Y(NO3 )3 .6H2 O, Eu(NO3 )3 ·5H2 O and AgNO3 . The USP process starts with
and Eu precursors, which provides a homogeneous mixture of both constituents. After that, they start
melting of the Y and Eu precursors, which provides a homogeneous mixture of both constituents.
to experience a stepwise thermal decomposition reaction simultaneously to form a hierarchical
After that, they start to experience a stepwise thermal decomposition reaction simultaneously to form
nanostructure.
a hierarchical During their thermal
nanostructure. Duringdecomposition, the Ag precursor
their thermal decomposition, the Agstarts to melt
precursor and,
starts through
to melt and, the
end of the Y and
through Eu nitrate
the end of the Ydecomposition reactions, thereactions,
and Eu nitrate decomposition Ag nitrate thestarts to decompose.
Ag nitrate This explains
starts to decompose.
the not well integrated and agglomerated Ag nanoparticles in the as-prepared
This explains the not well integrated and agglomerated Ag nanoparticles in the as-prepared samples samples (see Figure
18). Moreover,
(see Figure due to the fastdue
18). Moreover, heating
to theand
fast cooling rates,
heating and there rates,
cooling were theredefects,
were pores andpores
defects, poorand crystal
poor crystal
arrangement in arrangement
the as-prepared in thesamples.
as-prepared samples.
During theDuring the next
next stage stagetreatment,
- heat - heat treatment,
enough enough
time for
time for
diffusion wasdiffusion
provided was
and provided and better crystallisation
better crystallisation and slightand slight
crystal crystalwere
growth growth were observed.
observed. Moreover,
sinceMoreover,
Ag existssince as aAg existsatasaround
liquid a liquid1000
at around 1000 ◦homogeneous
°C, more C, more homogeneous and smoothand smooth
secondary secondary
particles
particles (see Figure 19) were observed with respect to the as-prepared ones.
(see Figure 19) were observed with respect to the as-prepared ones.
Figure 18.18.SEM
Figure SEMimage
imageof
of USP synthesisedAg/(Y
USP synthesised Ag/(Y Eu
0.95
0.95 Eu )2)O
0.05
0.05 2O nanocomposite.
3 3nanocomposite.
Materials 2020, 13, 3485 21 of 28
Figure 19.
Figure 19.SEM
SEMimage
image of
of heat-treated Ag/(Y
heat-treated Ag/(Y 0.95 Eu0.05)2O3 nanocomposite.
0.95 Eu0.05 )2 O3 nanocomposite.
Figure 19. SEM image of heat-treated Ag/(Y0.95 Eu0.05)2O3 nanocomposite.
The
The The mechanism
mechanism given
given ininin Figure 20was
Figure was proposed considering the thermochemical andandstructural
mechanism given Figure20 20 was proposed considering
proposed considering thethe thermochemical
thermochemical structural
and structural
characterisation
characterisation results.
results. TheThe USP process starts with melting of the Y and Eu precursors, which provides
characterisation results. TheUSP USPprocess
process starts withmelting
starts with meltingofof thethe Y and
Y and Eu Eu precursors,
precursors, whichwhich
a homogeneous
provides a mixturemixture
homogeneous of both constituents.
of both After that, After
constituents. they start,
that, simultaneously,
they start, to experience to
simultaneously,
provides a homogeneous mixture of both constituents. After that, they start, simultaneously, to
a stepwise thermal decomposition reaction to form a hierarchical nanostructure. During their
experience a stepwise
experience a stepwise thermal
thermaldecomposition reactiontotoform
decomposition reaction form a hierarchical
a hierarchical nanostructure.
nanostructure. DuringDuring
thermal decomposition, the Ag precursor starts to melt and, through the end of the Y and Eu nitrate
their thermal decomposition, the Ag precursor starts to melt and, through
their thermal decomposition, the Ag precursor starts to melt and, through the end of the Y and Eu the end of the Y and Eu
decomposition reactions, the Ag nitrate starts to decompose. This explains the not well integrated and
nitrate
nitrate decomposition
decomposition reactions,the
reactions, the Ag
Ag nitrate
nitrate starts
startstotodecompose.
decompose. This explains
This explainsthe not
the well
not well
agglomerated Ag nanoparticles in the as-prepared samples (See Figure 18). Moreover, due to the fast
integrated
integrated and agglomerated Ag nanoparticles in the as-prepared samples (See Figure 18). Moreover,
heatingandandagglomerated
cooling rates, there Ag nanoparticles in theand
were defects, pores as-prepared
poor crystalsamples (See Figure
arrangement 18). Moreover,
in the as-prepared
due to the fast heating and cooling rates, there were defects, pores and poor crystal arrangement in
due to the fast
samples. heating
During the and
heat cooling
treatment, rates,
enoughthere
timewere defects, was
for diffusion pores and poor
provided and crystal arrangement in
better crystallisation
the as-prepared samples. During the heat treatment, enough time for diffusion was provided and
the as-prepared
and slight samples.
crystal growth During the heatMoreover,
treatment, enough time
as afor diffusion was provided
◦ more and
better crystallisation and were
slightobserved.
crystal growth weresince Ag exists
observed. Moreover, liquid at around
since Ag exists 1000
as aC,
liquid
better
at crystallisation
homogeneous
around 1000and °C,and
smooth
moreslight crystalparticles
secondary
homogeneous growth were observed.
and formed
smooth (see FigureMoreover,
secondary 19). Moreover,
particles since
formed Ag
(seeexists
a significant as19).
a liquid
primary
Figure
crystal growth of Eu 3+ :Yprimary
O3 wascrystal
observed, which implies
at around
Moreover,1000 °C, more
a significant 2homogeneous and
growth smooth
of Eu Othat
3+:Y2secondaryAg didparticles
not hinderformed
the mobility
(see of
3 was observed, which implies that Ag did
grain 19).
Figure
boundaries,
Moreover,
not hinder since
a significant it
the mobilityexists
primary as liquid.
of graincrystal growth
boundaries, of it
since Euexists
3+ :Y2Oas3 was observed, which implies that Ag did
liquid.
not hinder the mobility of grain boundaries, since it exists as liquid.
Figure 20.
Figure Formation mechanism
20. Formation mechanism of
of as-prepared
as-prepared and
andheat-treated
heat-treatedAg/(Y
Ag/(Y0.95 Eu 0.05))22OO3 3nanocomposites
0.95 Eu0.05
nanocomposites
adapted from [106].
adapted from [106].
Consequently,
Figure 20. Formationdue to the fastofnature
mechanism of the and
as-prepared USPheat-treated
fast heatingAg/(Y
rates 0.95
and Eushorter reaction times,
0.05)2O3 nanocomposites
heat treatment following
adapted from [106]. synthesis is highly required to provide uniform distribution of the
constituents. Higher Ag concentrations of the as-prepared samples resulted in emission quenching
and yielded poordue
Consequently, luminesce. However,
to the fast natureAg of enhanced emission
the USP fast was rates
heating observedand within
shorterheat-treated
reaction times,
heat treatment following synthesis is highly required to provide uniform distribution of the
Materials 2020, 13, 3485 22 of 28
Consequently, due to the fast nature of the USP fast heating rates and shorter reaction times, heat
treatment following synthesis is highly required to provide uniform distribution of the constituents.
Higher Ag concentrations of the as-prepared samples resulted in emission quenching and yielded
poor luminesce. However, Ag enhanced emission was observed within heat-treated samples. Then,
2.5 wt. % Ag incorporation followed by 2 h heat treatment at 1000 ◦ C is reported as the most promising
red light-emitting phosphors’ synthesis conditions via USP.
7. Conclusions and Outlook

From the presented review the following conclusions can be summarised:
(1) USP is a potentially reliable method for the large scale synthesis of nanoparticles; (2) The size
of obtained nanoparticles is connected with the droplet diameter and the initial concentration of
the precursor solution; (3) In USP, in general, there are two conversion formation mechanisms
of nanoparticles: DTP and GTP; (4) Through USP it is possible to synthesise AuNPs, particles
decorated with nanoparticles (Ag/TiO2 and Au/TiO2 ), Au/Fe2 O3 nanoparticles, photoluminescent
Ag/(Y0.95 Eu0.05 )2 O3 nanoparticles and others, in the form of powder or in solution as a suspension;
(5) Characterisation of nanoparticles synthesised through USP is complex, and is connected closely
to the different techniques, such as SEM, STEM, TEM, EDX analysis and others, with the aim of
obtaining information about size, morphology, chemical composition and possible functional properties
of nanoparticles.
It is important to take into account that the USP is a very fast process where all the described
processes take place in micrometres’ volume and in parts of seconds. For these reasons, the deviations
of the proposed models are possible, and, based on this, synthesised nanoparticles are very often
in a metastable state. The speed of the process and its reaction mechanisms also prevent real-time
observations of the particle formation, while the many chemical and physical species present in the
reaction tube (simultaneously present droplets of various sizes, vapours of solvents and salts) make
modelling of the formation mechanisms difficult. This requires multiple optimisation experiments in
order to obtain the desired particle characteristics, as the material properties are affected by several
parameters. The formation models are, as such, derived from the characterisation of the finally obtained
particles, while the connections between the parameters and the material properties are frequently not
complete. More advanced characterisation technologies could alleviate this issue and provide more
insight into the formation mechanisms, in order to reduce the number of optimisation experiments.
This is especially important with upscaled USP devices, for reducing the costs of production set up.
An advantage of USP is its ability to produce complex morphologies and compositions in a
one-pot synthesis method, with a continuous production, and is a reasonable development direction
of the USP. This ability gives USP the potential for greater uptake in electronic, energy devices, solar
cells and photocatalysis [40,52]. However, complex particles again increase the number of required
optimisation steps and experiments to obtain the desired particle properties.
The rapid formation at elevated temperatures may also result in undesired properties of the final
particles, such as crystallinity, composition or morphology. In some cases, subsequent thermal or
chemical treatment of the particles produces the desired result, however, this decreases the advantage of
using USP as a one-pot synthesis method, increasing particle production complexity and costs. In some
cases, optimisation of the USP parameters and formation conditions can produce more favourable
results without additional processing.
Author Contributions: Conceptualisation, P.M. and R.R.; methodology, P.M.; software, P.M.; validation, R.R.;
formal analysis, P.M.; resources, R.R.; writing—original draft preparation, P.M.; writing—review and editing,
R.R.; supervision, R.R.; funding acquisition, R.R.; All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by the Slovenian Research Agency, Infrastructure Core Funding I0–0029.
Conflicts of Interest: The authors declare no conflict of interest.
Materials 2020, 13, 3485 23 of 28
Abbreviations
AuNP gold nanoparticle
DTP Droplet-To-Particle
EDX Energy-Dispersive X-ray spectroscopy
GTP Gas-To-ParticleFigure
PL Photoluminescent
SEM Scanning Electron Microscopy
STEM Scanning Transmission Electron Microscopy
TEM Transmission Electron Microscopy
USP Ultrasonic Spray Pyrolysis
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© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
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Keywords: Ultrasonic Spray Pyrolysis; Nanotechnology; noble metals nanoparticles; formation

Materials 2020, 13, 3485; doi:10.3390/ma13163485 www.mdpi.com/journal/materials

2. Ultrasonic Spray Pyrolysis

Particle Production Method Typical Particle Sizes Possible Production Yield

Materials 2020, 13, x FOR PEER REVIEW 4 of 28

Figure 1.1. Aerosol

Materials 2020, 13, 3485 12 of 28

4.3. Gold Nitrate Precursor

4.3. Gold Nitrate Precursor

Figure 12. TEM

5.1. Ag/TiO22 and

Figure 15. Metal/oxide nanoparticles’ formation model, adapted from [37].

5.1.3. Ag/TiO2 and Au/TiO2 Nanoparticles’ Formation Model

5.2. Au/Fe2 O3 Nanoparticles

Figure 16. Comparison

Materials 2020, 13, x FOR PEER REVIEW 21 of 28

7. Conclusions and Outlook

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