Nanomaterials 10 02317

nanomaterials
Review
Nanoparticles Engineering by Pulsed Laser Ablation
in Liquids: Concepts and Applications
Enza Fazio 1, * , Bilal Gökce 2 , Alessandro De Giacomo 3,4 , Moreno Meneghetti 5 ,
Giuseppe Compagnini 6 , Matteo Tommasini 7 , Friedrich Waag 2 , Andrea Lucotti 7 ,
Chiara Giuseppina Zanchi 7 , Paolo Maria Ossi 8 , Marcella Dell’Aglio 4 , Luisa D’Urso 6 ,
Marcello Condorelli 6 , Vittorio Scardaci 6 , Francesca Biscaglia 5 , Lucio Litti 5 , Marina Gobbo 5 ,
Giovanni Gallo 1 , Marco Santoro 9 , Sebastiano Trusso 10 and Fortunato Neri 1
1 Department of Mathematical and Computational Sciences, Physics and Earth Physics, University of Messina,
Viale F. Stagno D’Alcontres 31, I-98166 Messina, Italy; [email protected] (G.G.); [email protected] (F.N.)
2 Department of Technical Chemistry I and Center for Nanointegration Duisburg-Essen, University of
Duisburg-Essen, Universitätsstrasse 7, 45141 Essen, Germany; [email protected] (B.G.);
[email protected] (F.W.)
3 Department of Chemistry, University of Bari, Via Orabona 4, 70126 Bari, Italy;
[email protected]
4 CNR-NANOTEC, c/o Department of Chemistry, University of Bari, Via Orabona 4, 70126 Bari, Italy;
[email protected]
5 Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova, Italy;
[email protected] (M.M.); [email protected] (F.B.); [email protected] (L.L.);
[email protected] (M.G.)
6 Department of Chemical Sciences, University of Catania, V.le A. Doria 6, 95125 Catania, Italy;
[email protected] (G.C.); [email protected] (L.D.); [email protected] (M.C.);
[email protected] (V.S.)
7 Department of Chemistry, Materials, Chemical Engineering, Politecnico di Milano, Piazza Leonardo da
Vinci 32, I-20133 Milano, Italy; [email protected] (M.T.); [email protected] (A.L.);
[email protected] (C.G.Z.)
8 Department of Energy & Center for NanoEngineered Materials and Surfaces—NEMAS,
Politecnico di Milano, Piazza Leonardo da Vinci 32, I-20133 Milano, Italy; [email protected]
9 STMicroelectronics S.R.L., Stradale Primosole 37, 95121 Catania, Italy; [email protected]
10 CNR-IPCF Istituto per i Processi Chimico-Fisici, 98053 Messina, Italy; [email protected]
* Correspondence: [email protected]; Tel.: +39-090-676-5394

Received: 28 September 2020; Accepted: 16 November 2020; Published: 23 November 2020
Abstract: Laser synthesis emerges as a suitable technique to produce ligand-free nanoparticles, alloys
and functionalized nanomaterials for catalysis, imaging, biomedicine, energy and environmental
applications. In the last decade, laser ablation and nanoparticle generation in liquids has proven to
be a unique and efficient technique to generate, excite, fragment and conjugate a large variety
of nanostructures in a scalable and clean way. In this work, we give an overview on the
fundamentals of pulsed laser synthesis of nanocolloids and new information about its scalability
towards selected applications. Biomedicine, catalysis and sensing are the application areas mainly
discussed in this review, highlighting advantages of laser-synthesized nanoparticles for these types of
applications and, once partially resolved, the limitations to the technique for large-scale applications.
Keywords: colloids; laser synthesis; plasmonics; sensing; biomedicine; catalysis; pollutants
Nanomaterials 2020, 10, 2317; doi:10.3390/nano10112317 www.mdpi.com/journal/nanomaterials

Nanomaterials 2020, 10, 2317 2 of 50
1. Introduction
The intrinsic properties of nanoparticles (NPs), possibly combined with other materials,
disclose many applications where one can achieve miniaturization (e.g., of electronic equipment),
weight reduction (as a result of an increased material efficiency) and/or improved functionalities of
materials (e.g., higher durability, conductivity, thermal stability, solubility, reduced friction, selective
molecular detection) [1,2]. The remarkable size-tunable properties of nanomaterials produced by
laser–matter interaction (e.g., size distribution, agglomeration state/dispersion, crystal structure,
surface area and porosity, surface charge, shape/morphology, dissolution/solubility) make them a hot
research topic in material science, with far-reaching applications, ranging from quantum computers to
cures for cancer [3,4].
Bottom-up and top-down procedures are the two approaches used for the synthesis of
nanomaterials [5]. The first include the miniaturization of materials and components (up to
the atomic level) with subsequent self-assembling that leads to the formation of nanostructures.
Typical examples are the formation of quantum dots during epitaxial growth, or the production
of NPs as colloidal dispersions by chemical approaches [6]. Instead, top-down approaches use
macroscopic starting structures that are externally controlled by the processing down to nanostructures.
Typical examples are etching (controlled by masks), ball milling, metal-organic vapor phase epitaxy
and the application of severe plastic deformations [7].
There are many literature papers on laser interaction with hard, soft and smart materials, targeting
future applications in the fields of energy production (nano-energy) and biomedicine [8], as well as
recent progress in the understanding of the fundamental mechanisms involved in laser processing [9].
Such laser techniques are interesting in many regards, as they enable the processing of photovoltaic
cells [10], thermoelectric materials and devices [11], micro and nanosystems for energy storage and
conversion [12,13], biodegradable and biocompatible NPs for food packaging [14] as well as vectors for
drug and gene delivery [15,16]. The interest towards pure and electrostatically stabilized nanocolloids
is well recognized [17–21]. Although nanotechnologies and nanomaterials have much potential to
introduce innovative products and production processes in the food industry and in the biomedical
field, they are facing major challenges in being cost-effective in the production of e.g., edible and
nontoxic nano-delivery systems, or effective formulations that are safe for human consumption and
drug treatments [22].
Laser synthesis of colloids, powered by robust, high-power lasers, appears to be a key enabling
process that is chemically clean and environmentally friendly, and appealing [23,24] for industrial
manufacturing of functional nanomaterials while being useful in many different areas, such as:
hydrogen generation [16], hydrogen storage [25], heterogeneous catalysis using colloidal high-entropy
alloy NPs [26,27], anticancer [28] and antimicrobial [29] research, drug monitoring [30], additive
manufacturing applications [31,32], and nonlinear nanophotonics [33]. In addition, NPs prepared by
the Laser Ablation in Liquids (LAL) have been recently used for various and unique applications like
friction reduction [34], solar nanofluids [35,36], optical limiting devices [37,38] and so on.
The generation of NPs with LAL still has some challenging aspects, such as the fabrication of NPs
with a specific size and shape, the reduction of polydispersity and the increase of productivity [39].
Despite some unsolved problems of a physical, chemical and technical nature, several strategies have
been proposed to overcome the above issues, including the selection of the appropriate liquid or
stabilizing agent, the optimization of the focusing conditions and liquid levels, as well as the adoption
of scanning and fluid dynamics strategies by different liquid handling configurations [40–44] and the
postirradiation of colloids [45].
To explore the wide range of opportunities that LAL brings, the unique properties of femtosecond
lasers is a further hot research topic, not only to increase NP production, but also to generate structural
modifications and new material phases [46,47]. As reported by Streubel et al. [48], low productivity
shortcomings in LAL have been almost entirely remedied, reaching NP production rates of several
grams per hour. In addition to LAL, Laser Melting in Liquids (LML), Laser Fragmentation in Liquids
Nanomaterials 2020, 10, x 3 of 50
offer alternative routes to obtain colloids with controlled NP sizes. Nevertheless, an industrial series
product, or manufacturing process based on laser-synthesized particles is yet to come. Together with
the development
Nanomaterials 2020, 10,of2317
new strategies to increase NP productivity, future efforts should be directed
3 ofto
50
further improve the surface properties of the produced NPs, since each application requires a
different surface/interface chemistry. This would ensure reaching an advanced stage in those
(LFL) as well as pulsed Laser Photoreduction/oxidation in Liquids (LPL), offer alternative routes to
applications where the surface processes determine the performance of the final devices [49].
obtain colloids with controlled NP sizes. Nevertheless, an industrial series product, or manufacturing
In this review, we first give an overview of the fundamentals of pulsed laser ablation synthesis.
process based on laser-synthesized particles is yet to come. Together with the development of new
Moreover, we aim to display a combined picture of the several processes implied by LAL [50,51],
strategies to increase NP productivity, future efforts should be directed to further improve the surface
remarking, with respect to previous reviews [23,39,52–54], the high complexity and multiple time-
properties of the produced NPs, since each application requires a different surface/interface chemistry.
scale transient physics and chemistry typical of LAL. We point at this target by taking into account
This would ensure reaching an advanced stage in those applications where the surface processes
different experimental conditions. The fundamental mechanisms of LAL are analyzed in depth, to
determine the performance of the final devices [49].
stimulate concepts that are suitable to develop high performance devices based on the peculiar
In this review, we first give an overview of the fundamentals of pulsed laser ablation synthesis.
properties that the nanomaterials produced by LAL can offer. In the second part of this review, we
Moreover, we aim to display a combined picture of the several processes implied by LAL [50,51],
outline selected applications of LAL in biomedicine, catalysis and sensing. We outline the advantages
remarking, with respect to previous reviews [23,39,52–54], the high complexity and multiple time-scale
of laser synthesized NPs for these applications (see Figure 1) and the issues that have to be solved to
transient physics and chemistry typical of LAL. We point at this target by taking into account different
approach the high degree of process control that is required in industrial applications.
experimental conditions. The fundamental mechanisms of LAL are analyzed in depth, to stimulate
Throughout the review we pointed at two main objectives. First, to offer an analytical overview
concepts that are suitable to develop high performance devices based on the peculiar properties
that is updated and complete on the principles of LAL method, as well as on the role that is played
that the nanomaterials produced by LAL can offer. In the second part of this review, we outline
on the synthesis of NPs by process parameters, both laser and geometry related, and by the effects
selected applications of LAL in biomedicine, catalysis and sensing. We outline the advantages of laser
specifically depending on the liquid. Second, we describe the applications we presently believe are
synthesized NPs for these applications (see Figure 1) and the issues that have to be solved to approach
most promising in the field: these include plasmonic-related sensing and nanomedicine, and
the high degree of process control that is required in industrial applications.
catalysis.
Figure
Figure1.1.Schematic showing
Schematic showingthethe
outline of the
outline of review. FromFrom
the review. the fundamentals and up-scaling,
the fundamentals in the
and up-scaling,
center, arrowsarrows
in the center, point outwards to the four
point outwards to theapplication areas. areas.
four application
2. LALThroughout
Synthesisthe review we
Methods: pointedProcess
Principle, at two main objectives.
Parameters andFirst, to offer
Liquids an analytical
Effects overview
on Nanoparticle
that is
Formationupdated and complete on the principles of LAL method, as well as on the role that is played
on the synthesis of NPs by process parameters, both laser and geometry related, and by the effects
specifically
2.1. Mechanismdepending on Laser
in ns-Pulsed the liquid. Second,
Ablation we for
in Liquid describe the applications
the Production of Metallicwe presently
Nanopar believe are
ticles
most promising in the field: these include plasmonic-related sensing and nanomedicine, and catalysis.
Laser Ablation in Liquid (LAL) for the production of nanostructures is based on the ejection of
material by a laser pulse irradiating a solid target immersed in liquid. The laser matter interaction
2. LAL Synthesis Methods: Principle, Process Parameters and Liquids Effects on

Nanoparticle Formation
2.1. Mechanism in ns-Pulsed Laser Ablation in Liquid for the Production of Metallic Nanoparticles
Laser Ablation in Liquid (LAL) for the production of nanostructures is based on the ejection of
material by a laser pulse irradiating a solid target immersed in liquid. The laser matter interaction and
the consequent ablation are strongly dependent on the irradiance and the duration of the pulse, on the
and the consequent ablation are strongly dependent on the irradiance and the duration of the pulse,
background liquid, on the sample geometry and morphology as well as on the focusing condition.
on the background liquid, on the sample geometry and morphology as well as on the focusing
A full description of the LAL, at different experimental conditions, is beyond the scope of this paper
condition. A full description of the LAL, at different experimental conditions, is beyond the scope of
and the interested reader can refer to the following review papers: [39,52,55], and references therein.
this paper and the interested reader can refer to the following review papers: [39,52,55], and
Here, in order to offer a general viewpoint on the complexity of the sequence of the processes involved
references therein. Here, in order to offer a general viewpoint on the complexity of the sequence of
in LAL, ns-LAL, for the production of metal NPs in water, will be discussed.
the processes involved in LAL, ns-LAL, for the production of metal NPs in water, will be discussed.
As it has been clearly established, ns-PLAL is based on a sequence of different processes:
As it has been clearly established, ns-PLAL is based on a sequence of different processes: laser
laser ablation and plasma induction, energy exchange from plasma to the liquid and consequent
ablation and plasma induction, energy exchange from plasma to the liquid and consequent
generation of the cavitation bubble and release of particles from the bubble to the solution. In Figure 2
generation of the cavitation bubble and release of particles from the bubble to the solution. In Figure
the different LAL steps are summarized.
2 the different LAL steps are summarized.
Figure 2.2. Different

Figure Different steps
steps of
of Laser
Laser Ablation
Ablation inin Liquid
Liquid (LAL).
(LAL). The
The picture
picture of
oflaser-matter
laser-matter interaction
interaction
refers to
refers to aa ns-laser
ns-laser focused
focused onon Pt
Pt target
target in
inwater.
water. The
The plasma
plasma andand bubble
bubble images
images and
and volumes
volumes as as
functions of the delay time since the laser pulse have been acquired with optical emission
functions of the delay time since the laser pulse have been acquired with optical emission imaging and imaging
and shadowgraphy,
shadowgraphy, respectively
respectively (Al target
(Al target in MilliQ
in MilliQ water, water,
Elaser =E270
laser = 270 mJ, laser crater size = 1.6 ± 0.2
mJ, laser crater size = 1.6 ± 0.2 mm,
mm, λ laser = 532 nm, laser pulse duration = 6 ns, laser frequency = 10 Hz). The nanoparticles (NPs)
λlaser = 532 nm, laser pulse duration = 6 ns, laser frequency = 10 Hz). The nanoparticles (NPs) visible
visible
in cuvettein cuvette and micrograph
and micrograph image are image are Au NPs.
Au NPs.
Laser-matter interaction:
Laser-matter interaction:TheThebasic
basicmechanisms
mechanisms inducing
inducing the the laser
laser ablation
ablation inin liquid,
liquid, as
as well
well as
as
their dependence on laser pulse
their dependence on laser pulse properties,properties, do not differ notably, with respect of laser
notably, with respect of laser ablation inablation in
gaseous environment
gaseous environment [54].[54]. In
In the
the case
case ofof ns-laser
ns-laser ablation,
ablation, just
just aa portion
portion of of the
the laser
laser pulse
pulse reaches
reaches
directly the
directly the target
target surface,
surface, while
while most
most of of the
the laser
laser pulse
pulse is is spent
spent in in electron
electron heating
heating by by inverse
inverse
bremsstrahlung. This implies that the ablated material is converted to a plasma phase duringlaser
bremsstrahlung. This implies that the ablated material is converted to a plasma phase during the the
pulsepulse
laser irradiation. Differently
irradiation. to what
Differently to whatcancan
be beobserved
observed in ina agas
gasbackground
backgroundenvironment,
environment, as aa
consequence of
consequence of the
the water
water incompressibility,
incompressibility, the the ablated
ablated material
material is is strongly
strongly confined
confined andand in
in turn
turn
reaches high
reaches high density.
density. This
This effect
effectdecreases
decreasesthe thepenetration
penetrationof of the
the laser
laser through
through thethe plasma
plasma during
during thethe
initial stage
initial stage of
of expansion,
expansion, inducing
inducing thethe propagation
propagation of of gradient
gradient of of temperature
temperature in in the
the ejected
ejected material,
material,
i.e the
i.e the plasma.
plasma. ForFor what
what concerns
concerns the
the type
type ofof target
target used,
used, itit should
should be be considered
considered thatthat morphological,
morphological,
electrical and
electrical and optical
opticalproperties
propertiesofofthethetarget
targetaffect thethe
affect initial interaction
initial interaction of the
of material
the materialwithwith
the laser
the
laser pulse. For example, a metallic target allows the use of lower ablation irradiance with respectthe
pulse. For example, a metallic target allows the use of lower ablation irradiance with respect to to
semiconductor, if we neglect the difference in reflectivity. In any case if an irradiance well above the
breakdown threshold is used, the ablation can be assumed congruent, and similar plasma behavior
can be observed.
The mechanisms concerning the evolution of the ejected material after laser ablation are strongly
correlated to the duration of the laser pulse. Ideally, with a laser pulse with a shorter duration than a
the semiconductor, if we neglect the difference in reflectivity. In any case if an irradiance well above
the breakdown threshold is used, the ablation can be assumed congruent, and similar plasma behavior
can be observed.
The mechanisms concerning the evolution of the ejected material after laser ablation are strongly
correlated to the duration of the laser pulse. Ideally, with a laser pulse with a shorter duration than a
few tens of fs, the effect of the interaction of the laser pulse with the ejected material can be neglected
and the evolution of the ablated material can be investigated with atomistic models [56]. On the
contrary, when the laser pulse is long enough (as in the case of ns) to effectively interact with the
ablated material, inducing further ionization and electron heating, the role of the plasma becomes
dominant and kinetics models coupled with fluidynamics are required for a full description of the
phenomenon [57]. In this review, when describing fundamental aspects, we will refer to ns-ablation,
while a brief discussion on ultrashort ablation is reported in Section 2.2.
Plasma phase: The plasma phase plays an important role during ns-LAL because the plasma is the
source of material that allows the formation of NPs. Plasma phase during ns-LAL can be investigated
with Optical Emission Spectroscopy (OES) in order to estimate the plasma parameters such as electron
number density, Ne , atomic number density, Na , and excitation temperature, T, as well as the features
of plasma dynamics after laser ablation. The emission spectrum of the Laser Induced Plasma (LIP)
under water is characterized mainly by continuum radiation with possibly some resonance peaks
of the element constituting the target [40]. The absence of the typical atomic spectral lines of the
LIP expanding in a gaseous environment is due to the high density reached by the ablated matter
under liquid confinement as discussed in [40–42]. In this case, the emission spectrum has a Planck-like
shape that has been ascribed to the radiative recombination and that in turn is proportional to the
blackbody law, although the spectrum is not related to any blackbody system. To better understand this
crucial point, let us consider blackbody (BB) power density in the Wiens’ approximation at hν/kT >> 1,
which is valid for the range 400–500 nm and T ~ 6000 K:
2hv3 1 2hv3 hv hv
Bv (v, T ) = 2 hv
≈ 2
exp (− ) ∝ v3 exp (− ) (1)
c exp ( ) − 1 c kT kT
kT
where h is the Planck constant, ν is the frequency, c is the light speed, k is the Boltzmann constant and T
is the temperature.
On the other hand, the radiative recombination power density is given by the following equation [6]:
r
3/2
2 h4 2 1
hv − (Ei − Ep )
ρR
p (v, T ) = 2 2p ( ) exp (− )σion (p, v)v3 Ne2 (2)
π m3/2
e c 2 kT kT
where me is the electron mass, Ei and Ep are the ionization energy and the energy of the atom in
the level p, respectively, Ne is the electron number density and σion (p, ν) is the photoionization
cross section.
Equation (2) can be arranged as:
r
3/2
R 2 h3 2 1 2 hv
3 hv − (Ei − Ep )
ρp (v, T ) = 2 2p ( ) σ ion ( p, v ) Ne exp (− ) (3)
π m3/2
e
kT c 2 kT
Considering the high density due to the plasma confinement in water, only a few levels are
available and they are very close to the ionization energy [43]:
hv − (Ei − Ep ) hv
exp (− ) ≈ exp (− ) (4)
kT kT
Consequently, Equation (3) becomes:

q
ρR ( ) = 2 h3 2 1 3/2 σ (p, v)N 2 hv3 exp (− hv ) =
p v, T 2 π m3/2 2p ( kT ) ion e c2 kT
q e
3 3/2
(5)
= π2 h3/2 2p2 ( kT
1
) σion (p, v)Ne2 Bv (v, T )
me
The photoionization cross section at high density conditions, shows a smooth dependence on
investigated in the visible range, i.e., 1–3 eV. In the frame of this assumption and since, at fixed time
wavelength [42], so that its contribution can be considered constant in the range of photon energy
Ne and T are constant, Equation (5) becomes:
investigated in the visible range, i.e., 1–3 eV. In the frame of this assumption and since, at fixed time Ne
 R (v,T ) = G(T, N ) B (v,T )
and T are constant, Equation (5) becomes:
p e v (6)
R
where G is a constant with respect to ρpwavelength
(v, T ) = G(T, atN e ) · Btime
each v (v, Tof) plasma lifetime since it represents (6)a
function depending on detection efficiency, on the electron number density and on plasma
where G is a constant
temperature, but notwith onrespect to wavelength
the wavelength. at each time
Therefore, withinof plasma lifetime since
the previous it representsby
approximation, a
function depending
integrating Equation (6)on  with dν, a Planck-like distribution can be obtained. This may justify the
detection efficiency, on the electron number density and on plasma temperature,
but not on the wavelength.
observation of the Planck-like Therefore, within the
distribution of previous
plasma approximation,
emission in several by integrating
experiments Equation (6)
[58–60]
with dν, a Planck-like distribution
although the plasma is not a blackbody. can be obtained. This may justify the observation of the Planck-like
distribution
Recentlyof temporally
plasma emission in several
and spatially experiments
resolved OES has [58–60]
been although the plasma
applied during LAL is fornottheaproduction
blackbody.
RecentlyNPs
of metallic temporally
in orderand to spatially
estimateresolved OES has been
the temperature andapplied
densityduring
maps LAL withfor datathe processing
production of as
metallic NPs in order to
described in detail in [60]. estimate the temperature and density maps with data processing as described
in detail in [60].
As an example, Figure 3 shows the temperature map of a plasma induced on an aluminum target
As an in
immersed example,
water. By Figure 3 shows the
the inspection temperature
of the figure it can map of a plasma
be observed thatinduced
in the core on an aluminum
of the plasma,
target immersed in water. By the inspection of the figure it can
where the number density is very high [60,61], there is a decrease in temperature beyondbe observed that in the core of the
the
plasma, where the number density is very high [60,61], there is a decrease in
condensation temperature of most of the metals. As a matter of fact, the high pressure of the plasma temperature beyond the
condensation temperature
at this condition, i.e., under of water
most of the metals. As
confinement, a matter
allows of fact, the high
for condensation pressure
at higher of the plasma
temperatures at
than
this condition, i.e., under water confinement, allows for condensation at
those in standard condition. This observation indicates that NPs can be formed in the bulk of the higher temperatures than
those
plasma in and
standard
not onlycondition. This observation
in the border of the plasmaindicates
where the that NPs can
plasma bedown
cools formed fastinasthe bulk of the
a consequence
plasma and not only in the border of the plasma where the plasma cools down
of the rapid exchange of energy between the plasma and the surrounding liquid. It may be assumed fast as a consequence of
the rapid exchange of energy between the plasma and the surrounding liquid.
that also the material on the plasma border condensates in particle, but being this zone of the plasma It may be assumed that
also
out the material on the
of equilibrium, plasma border
it produces condensates
particles in particle,
with various sizes butandbeing thisOn
shapes. zonetheofcontrary,
the plasma out of
particles
equilibrium, it produces particles with various sizes and shapes. On
formed in the bulk of the plasma, being the result of thermodynamic equilibrium between the the contrary, particles formed
in the bulkof
processes ofgrowth
the plasma, being
and the the result of
evaporation, thermodynamic
are characterized by equilibrium
a sphericalbetween
shape with the processes
narrow size of
growth and
distribution. the evaporation, are characterized by a spherical shape with narrow size distribution.
Figure
Figure 3. (a)Image
3. (a) Imageofof laser-induced
laser-induced plasma
plasma on on Al target
Al target immersed
immersed in water,
in water, acquired
acquired with
with ICCD
ICCD camera.
camera. (b) Plasma(b) temperature
Plasma temperature 2D mapascalculated
2D map calculated reported inas[43]
reported inin[43]
(Al target (Alwater,
MilliQ targetElaser
in
MilliQ water, E
= 270 mJ, laser laser = 270 mJ, laser crater size = 1 ± 0.2 mm, λ
crater size = 1 ± 0.2 mm, λlaser = 532 nm, laser pulse = 532 nm, laser pulse duration = 6
laser duration = 6 ns, laser frequency = 10ns,
laser
Hz, delay time =
frequency 10 ns,
= 40 Hz,gate
delay time==2040ns).
width ns, (c)
gate
3Dwidth = 20 ns).of (c)
representation 3D representation
plasma temperature inof(b).
plasma
temperature in (b).
The mechanism of growth in the plasma phase during ns-LAL has been investigated with a
theoretical model in [61] where the competition between thermodynamic condensation and
electrostatic growth has been investigated. The result shows that at the electron number density
usually found in ns-LIP in water, the charging of seeds and particles occurs at ps-time scale. This
observation suggests that as soon as small clusters are formed because of the high-density gradient
at the initial stage of laser ablation, electrons attach. Consequently, the particles become negatively
The mechanism of growth in the plasma phase during ns-LAL has been investigated with a
theoretical model in [61] where the competition between thermodynamic condensation and electrostatic
growth has been investigated. The result shows that at the electron number density usually found in
ns-LIP in water, the charging of seeds and particles occurs at ps-time scale. This observation suggests
that as soon as small clusters are formed because of the high-density gradient at the initial stage of laser
ablation, electrons attach. Consequently, the particles become negatively charged and attract ions in the
plasma. Electron charging and ion implantation allows the particles to grow until the rate of growth is
balanced by the evaporation process due to the high temperature in the plasma (4000–6000 K). In this
scenario, the equilibrium between electrostatic growth and thermodynamic evaporation set the NPs
dimensions and induces the typical spherical shape observed after the LAL process.
Recently it has been shown, that the charging effect of the plasma is involved also in the subsequent
steps of LAL process [62,63]. As a matter of fact, when the particle exits the plasma, it is still with an
excess of electrons. This charge, in the order of a few nC for the entire NPs production per laser shot,
allows the repulsion between the particles and preserves the NPs from massive aggregation.
The cavitation bubble: The fast transfer of energy from the plasma to the surrounding water
induces the formation of a thin layer of vapor around the plasma border with high temperature and
high pressure. In order to reach the equilibrium with the liquid, the vapor expands, producing a
cavitation bubble. In the upper part of Figure 4, an example of the temporal evolution of a laser-induced
bubble during silver ablation is reported. The bubble expands until it reaches the equilibrium with the
surrounding liquid. Due to the fast expansion, the liquid at the border of the cavitation is compressed
and when the pressure of the bubble reaches the minimum at the maximum of the expansion, the bubble
is compressed and its shrinking stage begins. During this stage, the bubble increases its pressure
again and impacts the target, eventually pushing back the material to the target surface. There are
several models describing the evolution of a laser-induced bubble [64,65]. Most of these descriptions
are based on a theoretical model simulating the bubble radius evolution, assuming the mass and
momentum conservation equations in the liquid phase, and that the vapor pressure inside the bubble
is balanced by the pressure on the liquid side of bubble wall [66]. As an example, neglecting the
evaporation/condensation effects as the time associated to bubble dynamics is shorter than that of these
processes, the Keller–Miksis formulation can be applied with the following equations [66]:
.
..
3 M .2 R d 2σ R
(1 − M)ρl RR + (1 − )ρl R = (1 + M + )(p g (t) − l − 4ηl − p∞ ) (7)
2 3 cl dt R R
where R is the radius of the bubble and each dot indicates a time derivative, ρl is the liquid water density,
M is the bubble-wall Mach number, cl is the sound speed in the liquid, pg and p∞ are, respectively,
the gas pressure inside the bubble and the background static pressure and σl and ηl are, respectively,
the surface tension and dynamic viscosity of liquid water. The equation can be resolved considering
the weakly compressible equation of state for the liquid density, and assuming an adiabatic van der
Waals equation of state for a spherical bubble so that the vapor pressure and temperature are related to
the radius by the following equations:
γ
2σl R3∞ − h3
p g (t) = (p∞ + )( 3 ) (8)
R R − h3
γ−1
R3∞ − h3
T (t) = T∞ ( ) (9)
R3 − h3
where R∞ is the radius at which the pressure inside the bubble corresponds to p∞ , h is the radius
determined by the excluded volume of the water molecules and γ = Cp /Cv = (2 + N)/N is the ratio of the
specific heats, with N the number of degrees of freedom. The model starts assuming the initial radius
equal to that of the laser spot and the gas inside the bubble in thermal equilibrium with the liquid.
Although this simulation does not take into account the interaction of laser-induced plasma with the
vapor inside the bubble, it provides an acceptable qualitative description of bubble evolution.
Figure 4. Time resolved shadowgraphy images of the laser induced bubble on Ag target immersed
Figure in 4. Time(a)resolved
water and the shadowgraphy imagesradius
corresponding bubble of thecompared
laser induced
with bubble on Ag
the number of target
ejectedimmersed
Ag NPs in
waterduring
(a) andthe bubble evolution (as calculated in [44]) (b). Experimental conditions: laser energy = 108 during
the corresponding bubble radius compared with the number of ejected Ag NPs mJ,
the bubble evolution
laser frequency = (as calculated
2 Hz, insize
laser crater [44])
= 1(b). Experimental
± 0.2 mm, ICCD gate conditions:
width = 20laser energy
µs and = 108 mJ, laser
5 accumulations
frequency = 2image.
for each Hz, laser crater size = 1 ± 0.2 mm, ICCD gate width = 20 µs and 5 accumulations for each
image.
As a result of the charging effect on the NPs produced in the plasma phase due to the electrostatic
repulsion, NP clouds expand as well. If the NPs store enough charge immediately after the plasma stage,
As a result of the charging effect on the NPs produced in the plasma phase due to the electrostatic
the induced electrostatic pressure can be higher than the pressure at the water/vapor boundary and
repulsion, NP clouds expand as well. If the NPs store enough charge immediately after the plasma
NPs exit from the cavitation bubble and are released in solution. Recently, this phenomenon has been
stage, the induced electrostatic pressure can be higher than the pressure at the water/vapor boundary
investigated in detail in [62] and it has been found that the two main streams of NPs ejection due to the
and NPs exit from
electrostatic the cavitation
repulsion bubble
within the particleand areinreleased
cloud the bubble in occurs
solution. Recently,after
immediately thisthe
phenomenon
beginning of has
been the
investigated in detail
expansion phase and,in
in [62] andextent,
a greater it has between
been found that the stage
the collapsing two main
and thestreams of NPs ejection
bubble rebound [62].
due toFigure 4 shows the number of ejected AgNPs during the cavitation bubble evolution compared with the
the electrostatic repulsion within the particle cloud in the bubble occurs immediately after
beginning of the bubble
the measured expansion phase
radius, usingand, in a greater
Equations extent,
(8) and (9). between
The number of the ejected
collapsing
AgNPs stage and the
has been
bubblecalculated
rebound as [62].
reported in [62].
Figure 4 shows the number of ejected AgNPs during the cavitation bubble
It would be important
evolution compared with the measured to underlinebubble
that theradius,
spherical NPsEquations
using with a size (8)
around
and 10–20 nm number
(9). The are not of
the only particles produced. Indeed, in terms
the ejected AgNPs has been calculated as reported in [62]. of mass, the fraction of material converted in this kind
of NPs is a minor component. Larger particles are produced at the border of the plasma during the
It would be important to underline that the spherical NPs with a size around 10–20 nm are not
energy exchange from plasma to the surrounding liquid as mentioned below. Other bigger NPs can be
the only particles produced. Indeed, in terms of mass, the fraction of material converted in this kind
the result of aggregation of the spherical NPs during the collapse stage of the bubble. The NPs that are
of NPs is a minor component. Larger particles are produced at the border of the plasma during the
not ejected because of the electrostatic repulsion can remain trapped in the bubble, therefore they can
energybe exchange from plasma
then compressed, becausetoofthe
the surrounding
high pressure liquid as mentioned
of the collapse below. Other
stage, rearranging theirbigger NPs
structure in can
be theaggregates
result of aggregation
composed byof the spherical
individual NPsNPs.
spherical during the collapse
Finally, stageresult
as an intrinsic of theofbubble.
the laserThe NPs that
ablation,
are not ejected because of the electrostatic repulsion can remain trapped in the bubble, therefore they
can be then compressed, because of the high pressure of the collapse stage, rearranging their structure
in aggregates composed by individual spherical NPs. Finally, as an intrinsic result of the laser
ablation, debris of several hundred of nm with the same morphology of the irradiated target can be
found on the bottom of the ablation cell.
2.2. Upscaling
debris of Laser
of several Synthesis
hundred of nm of with
Colloids
the same morphology of the irradiated target can be found on
the bottom of the ablation cell.
As can be derived from the previous section, understanding the mechanisms of a process enables
All the discussion here refers to ns laser ablation and it gives a simplified scenario of the processes
its control, which can then lead to a precise experimental design. This section reviews process
involved in the production of NPs of high quality in terms of size distribution and chemical purity of
parameters of LAL that are of great importance for the scale-up of this process [66]. Additionally,
the colloidal solution. In order to increase the production rate, in recent years, different approaches
cross-dependencies between the single parameters are pointed out.
have been developed based on K-Hz laser source, ultrashort laser pulse and target shape, as will be
discussed
2.2.1. in Section
Scaling 2.2. Factors for Laser Ablation in Liquids
and Control
2.2. Upscaling of Laser
LAL process Synthesisare
parameters of Colloids
initial, adjustable, and related to components of the process, which
are the laser, the components of the optical setup, the ablation chamber, the fluid flow elements, the
As can be derived from the previous section, understanding the mechanisms of a process enables
ablation target, and the liquid environment. The process result of interest is the NP productivity,
its control, which can then lead to a precise experimental design. This section reviews process
which can be defined as volume of product achieved in a defined irradiation time (considering energy
parameters of LAL that are of great importance for the scale-up of this process [66]. Additionally,
efficiency, additional reference values like the laser power become relevant as well). In literature, the
cross-dependencies between the single parameters are pointed out.
ablation rate is frequently used for productivity comparisons. It corresponds to the loss of target
volume achieved
2.2.1. Scaling and in a defined
Control irradiation
Factors for Lasertime. By assuming
Ablation a 100% conversion of ablated matter to
in Liquids
NPs, the definitions of productivity and ablation rate are identical.
LAL process parameters are initial, adjustable, and related to components of the process,
A process starts with the input of initial parameters and creates an output, which comprises the
which are the laser, the components of the optical setup, the ablation chamber, the fluid flow elements,
results. In between those process parameters and results, variables can be defined. They generally
the ablation target, and the liquid environment. The process result of interest is the NP productivity,
depend on multiple process parameters of different components of the setup and bundle their impact
which can be defined as volume of product achieved in a defined irradiation time (considering energy
on the process. The dependency graph shown in Figure 5 displays the compilation of the process
efficiency, additional reference values like the laser power become relevant as well). In literature,
parameters of LAL clustered and assigned to the different components of the LAL setup. In addition,
the ablation rate is frequently used for productivity comparisons. It corresponds to the loss of target
the cross-dependencies of parameters, found in the process variables, and finally the process result(s)
volume achieved in a defined irradiation time. By assuming a 100% conversion of ablated matter to
are also illustrated in the figure.
NPs, the definitions of productivity and ablation rate are identical.
The use of different colors supports the readability of the dependency graph. Each time two or
A process starts with the input of initial parameters and creates an output, which comprises
more parameters or variables interdepend, their colors add up. For example, the input parameter
the results. In between those process parameters and results, variables can be defined. They generally
pulse duration of the cluster laser influences directly the output productivity but also indirectly the
depend on multiple process parameters of different components of the setup and bundle their impact
variable intensity. The colors of pulse duration (green) and energy density (wine) add up to dark
on the process. The dependency graph shown in Figure 5 displays the compilation of the process
brown, which represents the variable intensity. In the following sections, the impact of single input
parameters of LAL clustered and assigned to the different components of the LAL setup. In addition,
parameters and also the assembled variables on the NP productivity are evaluated. Note that product
the cross-dependencies of parameters, found in the process variables, and finally the process result(s)
properties such as the particle size distribution also represent an output of the process but are not
are also illustrated in the figure.
considered in detail here.
Figure 5. Dependence
Dependence graphgraph of
of process
process parameters, arranged in component clusters, relevant to LAL
up-scaling. If
If not
not marked
marked differently
differently by an arrow, the flow goes from the left to the right in horizontal
direction and
andfrom
fromthethe outside
outside to inside
to the the inside in vertical
in vertical direction.
direction. Colors Colors were
were used used
only only
for an for an
improved
improved
overview. overview.
Reprinted Reprinted with permission
with permission from [66]. from [66].
Laser Wavelength: The laser wavelength essentially influences the ablation rate in LAL [54,67–
70]. All studies agree independently from the ablated matter, the chosen liquid and the used laser
The use of different colors supports the readability of the dependency graph. Each time two or
more parameters or variables interdepend, their colors add up. For example, the input parameter pulse
duration of the cluster laser influences directly the output productivity but also indirectly the variable
intensity. The colors of pulse duration (green) and energy density (wine) add up to dark brown,
which represents the variable intensity. In the following sections, the impact of single input parameters
and also the assembled variables on the NP productivity are evaluated. Note that product properties
such as the particle size distribution also represent an output of the process but are not considered in
detail here.
Laser Wavelength: The laser wavelength essentially influences the ablation rate in LAL [54,67–70].
All studies agree independently from the ablated matter, the chosen liquid and the used laser pulse
duration on a higher productivity by using IR laser light compared to UV or Vis. The laser fluence was
kept at identical or at least comparable values in all studies. However, LAL was applied as a batch
approach in all investigations, and NP-induced shielding due to Rayleigh scattering [71] most likely
caused the differences in productivity. In addition, a higher absorption cross-section is given for NPs of
nearly all metals at UV or Vis wavelengths compared to IR wavelengths [72]. This is strongly indicated
by the observed smaller NP diameters at shorter applied wavelengths [54,69,70], which may be the
result of fragmentation induced by subsequent laser pulses during batch-LAL.
Schwenke et al. [54] determined the product concentration during picosecond-pulsed LAL at
different process times for IR and Vis wavelengths and three different metals. They found that the
concentration was comparable for both wavelengths at short process times. However, it increased
differently with time or the NP concentration, and less strongly at short wavelengths in all cases.
These results clearly demonstrate the shielding effect of the colloidal NPs.
Semerok et al. [73] found higher ablation rates by using shorter wavelengths in the picosecond
and nanosecond-pulsed laser ablation in air for several metals. The ablation rate increased stronger
for most metals when switching from the Vis to the UV range then from the IR to the Vis range,
which was in good agreement with the interband absorption of the targets. Similar results were also
found by Stafe et al. [74]. Naturally, the individual light absorption properties of bulk materials should
influence the number of absorbed photons of different wavelengths and provide optimums for high
ablation rates. However, the optical properties of an irradiated surface significantly depend on its
temperature [75], roughness [76,77] and oxidation state/degree [78]. For example, Letzel et al. [79]
recently observed a significant increase in the productivity of the laser ablation of silver in water during
the first 250 laser pulses irradiating an initially smooth target surface. Temperature, roughness and
oxidation state/degree of the target surface change differently strong during LAL and depend strongly
on the ablated material. This limits the a priori choice of the most productive wavelength for LAL
according to the standard light absorption spectrum of the material to be ablated.
It may be concluded that higher ablation rates for metals generally occur at UV laser wavelengths
due to the interband absorption. However, the productivity at Vis and IR wavelengths can be
comparable. A strong dependence on the metal, the laser fluence and also the laser pulse duration exists.
In case of high colloidal concentrations, the higher absorbance of short wavelengths by the particles
can make LAL of metals at short wavelengths less productive. These relations are summarized in
Figure 6. Note that for semiconducting and dielectric materials the initial ablation rate in absence of a
light-extinction colloid can be higher at red and near IR wavelengths under specific conditions due to
differences in the ablation mechanism compared to metals [80,81].
Laser Fluence: The laser fluence or energy density describes the pulse energy penetrating the
area of the effective laser spot on the surface of the ablation target. A variation of the laser fluence
may be realized by either varying the pulse energy [67,70,71,82–90] or the spot area via the working
distance [67,85,91]. Different results by both procedures can occur due to variations of the beam
propagation within the liquid phase. Furthermore, the distribution of the laser energy density in the
spot of a Gaussian beam differs. Naturally, the ablation rate in LAL follows a logarithmic growth
when increasing the laser fluence of femtosecond [90], picosecond [82,88] and nanosecond [85] pulses.
It may be concluded that higher ablation rates for metals generally occur at UV laser
wavelengths due to the interband absorption. However, the productivity at Vis and IR wavelengths
can be comparable. A strong dependence on the metal, the laser fluence and also the laser pulse
durationNanomaterials
exists. In2020,
case of high colloidal concentrations, the higher absorbance of short11wavelengths
10, 2317 of 50
by the particles can make LAL of metals at short wavelengths less productive. These relations are
summarized inlow
At very Figure
values6.ofNote thatfluence,
the laser for semiconducting
a less productiveand dielectric
ablation regimematerials thewhich
prevails [82], initial
is ablation
rate in absence of a here.
not considered light-extinction colloid
The logarithmic can beishigher
dependence at red
also known forand
lasernear IR in
ablation wavelengths
a gaseous under
specific environment
conditions [91–95].
due to differences in the ablation mechanism compared to metals [80,81].
Figure 6. Schematic
Figure of the
6. Schematic laser
of the ablation
laser ofmetals
ablation of metals in liquids
in liquids at different
at different wavelengths
wavelengths inand
in absence (a) absence (a)
and presence (b) of colloidal particles. Equal energy densities were assumed for all laser
presence (b) of colloidal particles. Equal energy densities were assumed for all laser spots. The diagram spots. The
diagramin in(c) (linear scales for
(c) (linear both axes)
scales demonstrates
for both the effect of an increasing
axes) demonstrates colloidal
the effect of an concentration
increasing on colloidal
the NP productivity in LAL at different wavelengths. The trends shown in the diagram represent
concentration on the NP productivity in LAL at different wavelengths. The trends shown in the
the interpretation of the combined results of the discussed literature in Section 2.2.1. Reprinted with
diagrampermission
represent the interpretation of the combined results of the discussed literature in Section
from [66].
2.2.1. Reprinted with permission from [66].
The onset of the saturation occurs at lower laser fluences for shorter laser pulse durations [90],
which
Laser may be The
Fluence: due laser
to higher laser or
fluence intensities
energy and the related
density optical
describes thebreakdown
pulse energyof thepenetrating
liquid. the
The lowered thermal impact on the material, and therefore stronger independence of laser penetration
area of the effective laser spot on the surface of the ablation target. A variation of the laser fluence
depths and fluence at shorter laser pulse length, may also play a role here. In addition, the type of
may be the
realized
ablatedby eitherinfluences
material varying thetheonset
pulse ofenergy [67,70,71,82
the saturation –90] orrate
in the ablation the[83,85,92]
spot area via the working
by different
distancelaser
[67,85,91]. Different
fluence thresholds andresults by both
penetration procedures
depths. For example,canHahn occur
et al. due to variations
[83] could not increaseofthethe beam
productivity of the laser ablation of silver in water in the pulse energy range of 100 to 500 µJ but nearly
tripled the productivity of the ablation of cobalt by increasing the pulse energy from 100 to 200 µJ
before reaching saturation. The working distance was kept constant by the authors.
The conventional definition of productivity in LAL (volume ablation per time) used in this
manuscript can also be related to the applied laser energy. This extended definition allows an
assessment of the energy efficiency, which seems reasonable from an economic and ecological point
of view. Neuenschwander et al. [96] demonstrated theoretically and experimentally that a maximum
energy efficiency of ultrashort-pulsed laser ablation is reached at an optimum fluence, which is the
material-specific threshold fluence of laser ablation multiplied by e2 . While the authors of the previously
mentioned study focused on laser ablation in air, Streubel et al. [44] also verified the correlation for
laser ablation in liquids.
In conclusion, the volume ablation rate logarithmically scales with the laser fluence. The progress
of the logarithmic function further depends on the ablation mechanism, the surrounding liquid,
and the target material. If productivity in LAL is further related to the invested laser pulse energy,
an optimum fluence can be found. Figure 7 illustrates the typical dependency of the NP productivity
on the laser fluence.
Laser Pulse Duration: The mechanism of laser ablation crucially depends on the pulse duration.
The influence of moderate fluences on the ablation rate of metals in gaseous atmosphere can be well
described by the two-temperature model [97] for femtosecond and picosecond pulses and by a simple
evaporation model at longer durations [95]. Extensions and refinements of the two-temperature
model even allow accurate predictions of the ablation rate in the femtosecond-pulsed laser ablation
of dielectrics [98] or of the low-fluence regime in the picosecond-pulsed laser ablation of metals [99].
Exchanging the gaseous ambient by a liquid causes a more intense cooling of the ablation target and
material-specific threshold fluence of laser ablation multiplied by e . While the authors of the
previously mentioned study focused on laser ablation in air, Streubel et al. [44] also verified the
correlation for laser ablation in liquids.
In conclusion, the volume ablation rate logarithmically scales with the laser fluence. The
progressNanomaterials
of the logarithmic
2020, 10, 2317 function further depends on the ablation mechanism, the12surrounding of 50
liquid, and the target material. If productivity in LAL is further related to the invested laser pulse
energy, of
anthe
optimum
laser-induced fluence canwhich
plasma, be found. Figure
may affect 7 illustrates
the ablation process the typicalneither
but should dependency of the NP
change the
principal ablation mechanism
productivity on the laser fluence. nor invalidate the describing models.
Figure 7.Figure
Illustration of the
7. Illustration of laser ablation
the laser ablationofofmetals
metals ininliquids
liquids at different
at different fluences
fluences varied varied by the pulse
by the pulse
energy
energy (a) and(a)the
andworking
the working distance
distance (b).The
(b). The diagram
diagram inin (c)(c)
demonstrates
demonstrates how thehowfluence variationvariation
the fluence
caused by different initial spot sizes affects the NP productivity in LAL in the high-fluence regime.
caused by different initial spot sizes affects the NP productivity in LAL in the high-fluence regime. A
A Gaussian beam profile was assumed. In (c), both axes scale linearly. The trends shown in the
Gaussian beam profile was assumed. In (c), both axes scale linearly. The trends shown in the diagram
diagram represent the interpretation of the combined results of the discussed literature in Section 2.2.1.
represent
Thethe interpretation
arrow of the
and the less dense combined
(dashed) results
line style of the discussed
in (c) indicate literature in
the trend in productivity Section
induced by a2.2.1. The
arrow and theinitial
smaller less spot
dense (dashed)
size. Reprintedline
withstyle in (c)from
permission indicate
[66]. the trend in productivity induced by a
smaller initial spot size. Reprinted with permission from [66].
Conclusively, a strong impact of the pulse duration on the ablation rate exists. A fair experimental
comparison of the ablation rate with laser pulses with durations ranging from some 10 femtosecond to
Laser
somePulse
100 nsDuration: The mechanism
is not accessible due to the lack of of
laser ablation
suitable crucially depends
laser technology. However,on if athe pulse duration.
wide-range
The influence
variation ofofmoderate fluences
the pulse duration on the
would ablation
be possible rate of
(keeping themetals in gaseous
pulse energy atmosphere
constant), can be well
a more effective
described
usebyof the two-temperature
the energy of single lasermodel
pulses [97] foroccur
should femtosecond and picosecond
at shorter pulse durations duepulses and by a simple
to the reduced
heat loss. However, the optical breakdown of the liquid in front of
evaporation model at longer durations [95]. Extensions and refinements of the two-temperature the ablation target as well as
non-linear optical effects such as the optical Kerr leading to filamentation limits the applicable fluence
model even allow accurate predictions of the ablation rate in the femtosecond-pulsed laser ablation
stronger at shorter laser pulses due to their higher intensities.
of dielectricsRiabinina
[98] or of the[90]
et al. low-fluence
investigatedregime in the picosecond-pulsed
the NP productivity of the LAL of goldlaser ablationsodium
in an aqueous of metals [99].
Exchanging
citratethe gaseous
solution ambient
at different pulseby a liquid
durations causes
between 40afsmore
and 200intense
ps but a cooling of the of
constant fluence ablation
50 mJ/cmtarget
2. and
of the laser-induced plasma, was
An optimal productivity which may
found at aaffect the ablation
pulse duration of 2 ps.process but should
The authors expectedneither change the
a decrease
in the productivity at lower pulse durations to
principal ablation mechanism nor invalidate the describing models. be caused by the optical breakdown of the liquid.
A loss of productivity at higher pulse durations was expected to originate from heat losses in the
target and laser-induced shielding effects. During their experiments, the laser pulse repetition rate
was kept constant and the scanning speed was kept at zero, which makes shielding effects at longer
pulse durations realistic. Interestingly, Sakka et al. [100] also observed a decreasing ablation rate at an
increasing pulse duration during the nanosecond-pulsed laser ablation of copper in water, although
this effect did not occur during laser ablation in air. This finding confirms the origin of a negative
impact of an increasing pulse duration on the ablation rate in the presence of the liquid environment.
In another study, Dittrich et al. compared the absolute and power-specific productivity of LAL of gold
in water for a compact, a middle class and a high-end laser system [101]. The authors applied LAL in a
liquid flow and with sufficient laser scanning to limit shielding effects. They found that even though
the absolute productivity was the lowest for the low-power, compact laser system, power-specific
productivity was much higher compared to the other systems. All three laser systems differed in
the laser pulse duration, which was 1 ns for the compact, 5 ns for the middle-class and 3 ps for the
high-end laser system, respectively.
Further details on the effect of the pulse duration on the ablation rate can be derived from studies
on the laser ablation of metals in air and vacuum. Schille et al. [102] found a slight decrease in
the ablation rate of copper during an increase of the pulse duration from 200 fs to 4 ps. A further
increase of the pulse duration up to 10 ps significantly reduced the ablation rate. As demonstrated
by Jaeggi et al. [103], the threshold fluence for ablation increases and the penetration depth decreases
in the ablation of copper and steel in air when increasing the pulse duration from 10 ps to 50 ps.
Naturally, both effects negatively affect the ablation rate. If the pulse duration is further increased
from the picosecond to the few nanosecond time regime, the threshold fluence for ablation becomes
constant [104]. In addition, the ablation rate becomes independent from the optical penetration depths
at these longer pulse durations due to the more thermal ablation mechanism [94]. Minor changes in the
ablation rate can be assumed in the transition regime from picosecond to nanosecond pulse durations.
However, the thermal nature of the laser ablation intensifies at even longer pulse durations. Heat losses
get more dominant and the ablation rate is consequently reduced [105]. In addition, the lifetime of the
laser-induced plasma and the pulse duration act on a comparable time scale for laser pulses longer
than some ten or hundred nanoseconds, which intensifies a self-induced plasma shielding of single
laser pulses.
In conclusion, an optimum in the pulse duration for achieving a maximized ablation rate in
LAL exists. It is probably located in the order of single picoseconds [86]. As the productivity limitation
at lower pulse durations stems from the optical breakdown of the liquid, the optimum of the pulse
duration strongly depends on the laser intensity, wavelength and the liquid. Figure 8 illustrates the
thermal loss and the pulse self-shielding by its induced plasma in dependence on the pulse duration
regime. Furthermore, the dependence of the productivity on the pulse duration is shown qualitatively
by excluding the optical breakdown of the liquid. The optical breakdown finds consideration in the
following
Nanomaterials 2020, 10,section
x on the laser intensity. 13 of 50
Figure 8. Illustration of the laser ablation of metals in liquids at different pulse durations neglecting
non-linear effects. Thermal losses (a) and self-shielding by plasma (b) of pulses of different duration
Figure 8.regimes. The diagram
Illustration of the in (c) demonstrates
laser ablation ofhow the coupling
metals constant
in liquids of electrons
at different and phonons
pulse durations affects
neglecting
the NP productivity in LAL, depending on the laser pulse duration. A change of the coupling constant
non-linear effects. Thermal losses (a) and self-shielding by plasma (b) of pulses of different duration
was assumed to have no influence on other material properties. In (c), the y-axis scales linearly.
regimes. The
Thetrends
diagram in (c) demonstrates how the coupling constant of electrons and phonons affects
shown in the diagram represent the interpretation of the combined results of the discussed
the NP productivity in LAL,
literature in Section depending
2.2.1. on the
In (c), the arrow andlaser pulse
the less duration.
dense A change
(dashed) line of thethe
style indicate coupling
effect of aconstant
was assumed
longerto have no
coupling timeinfluence
of electronson other
and material
phonons of the properties.
target materialInon(c), the y-axisReprinted
productivity. scales linearly.
with The
permission from [66].
trends shown in the diagram represent the interpretation of the combined results of the discussed
literatureLaser
in Section 2.2.1.
Intensity: In (c),
Since theis arrow
there a tight and the lessbetween
connection dense (dashed) line style
laser intensity, laser indicate thepulse
fluence and effect of
a longer coupling
duration, time of electrons
a differentiation between and each phonons of is
contribution the target The
difficult. material
opticalonbreakdown
productivity.
of theReprinted
liquid
withenvironment,
permission from
which[66].
may significantly reduce the ablation rate, is usually related to the laser intensity.
Additionally, self-focusing of the laser beam may be induced by the optical Kerr effect and consequently
increase
Laser the laser
Intensity: intensity.
Since thereThis
is amay promote
tight filamentation
connection of thelaser
between laser beam or an optical
intensity, breakdown
laser fluence and pulse
of the liquid. However, the intensity thresholds needed for the optical breakdown of water and the
duration, a differentiation between each contribution is difficult. The optical breakdown of the liquid
filament formation are comparable for femtosecond-pulsed laser radiation [106]. For picosecond pulses,
environment, whichthreshold
the intensity may significantly reduce
for filamentation the ablation
is generally muchrate,
higher isthan
usually related
for the opticalto the laserof
breakdown intensity.
Additionally, self-focusing
water and of theonly
becomes comparable laser beam
at low may
focusing be [107].
angles induced
Thus, by the optical
filamentation Kerr
plays no effect and
or only
consequently increase the laser intensity. This may promote filamentation of the laser beam or an
a minor role in LAL.
As described
optical breakdown of theby NoackHowever,
liquid. and Vogel [108], the laser-induced
the intensity cascade
thresholds neededof ionization
for the must reach
optical a
breakdown
specific density of free electrons to provoke the breakdown of the liquid in dependence on the pulse
of water and the filament formation are comparable for femtosecond-pulsed laser radiation [106]. For
picosecond pulses, the intensity threshold for filamentation is generally much higher than for the
optical breakdown of water and becomes comparable only at low focusing angles [107]. Thus,
filamentation plays no or only a minor role in LAL.
As described by Noack and Vogel [108], the laser-induced cascade of ionization must reach a
duration and wavelength. It is thus a competition of the recombination and ionization rate of free
electrons, ions and atoms. Due to higher electron densities, plasmas induced by nanosecond laser
pulses more effectively shield later irradiation than plasmas induced by picosecond pulses or long
femtosecond pulses [109]. Additionally, one to two magnitudes of higher intensity thresholds for
the optical breakdown of water are valid for femtosecond (1012 W/cm2 ) compared to nanosecond
(1010 W/cm2 ) pulses.
The intensity threshold for the optical breakdown of the liquid environment further depends on
the chemical nature and the purity of the liquid. In the case of linear hydrocarbons, Fujii et al. [110]
found a decrease in the breakdown threshold for an increasing chain length or molecular weight
using IR, nanosecond pulses. This is probably due to the increasing absorption cross-section of
the hydrocarbons. The threshold intensities for the optical breakdown of different hydrocarbon
aromatics at IR, nanosecond pulses are in the order of 1012 W/cm2 [111]. Kovalchuk et al. [112]
demonstrated, temporally and spatially resolved, how particulate impurities in tap water and different
alcohols act as seeds for the plasma formation in the laser-induced optical breakdown of the liquids.
In addition, the presence of soluble species also significantly reduces the intensity threshold of a liquid
for its breakdown [113,114]. It must be assumed that NPs act as solutes or impurities in this context.
In addition, breakdown seeds may also be introduced into liquids by complexation of solvent molecules
with dissolved gases [115].
In conclusion, the optical breakdown of the liquid environment in absence of an ablation target must
Nanomaterials 2020, 10, x for the applied laser parameters in LAL. Thereby it needs to be considered that colloidal
be excluded 14 of 50
particles and dissolved species reduce the breakdown threshold. Whether an optical breakdown of
the liquid occurs during LAL should therefore always be checked experimentally. Figure 9 illustrates
Figure 9 illustrates howbreakdown
how the optical the opticalof thebreakdown of the
liquid influences theproductivity
liquid influences the productivity
of LAL. Variations of the pulse of LAL.
Variations of the pulse duration and colloidal concentration
duration and colloidal concentration were considered. were considered.
Figure 9. Illustration of the optical

Figure 9. Illustration breakdown
of the optical breakdownof theliquid
of the liquid during
during theablation
the laser laser ablation
of metals inof metals in
liquids at different intensities neglecting non-linear effects. Dependence of
liquids at different intensities neglecting non-linear effects. Dependence of the occurrence the occurrence of the of the
optical breakdown on the laser pulse duration (a) and on the colloid concentration (b). Reprinted with
optical breakdown on the laser pulse duration (a) and on the colloid concentration (b). Reprinted with
Spatial Inter-Pulse Distance: The interaction of laser pulses with laser-induced plasma, bubble and
particle species limits the NP productivity in LAL. Whereas the shielding of a laser pulse by the
Spatialself-induced
Inter-Pulse Distance: The interaction of laser pulses with laser-induced plasma, bubble
plasma can only be reduced by using shorter pulse lengths, shielding effects induced
and particlebyspecies
previouslimits the NP
laser pulses productivity
can be in LAL.
reduced procedurally. TheWhereas
strategy is the shielding
to spatially of successive
separate a laser pulse by the
self-inducedlaser
plasma
pulsescan only bethe
by adjusting reduced
interplayby using
of the laser shorter
spot size, pulse lengths,
the scanning speedshielding effects induced by
(relative movement
between laser beam and target) and the pulse repetition rate to avoid shielding caused by the previous
previous laser pulses can be reduced procedurally. The strategy is to spatially separate successive
pulse [82,84,90,91,116].
laser pulses by Sattari
adjusting thefound
et al. [84] interplay ofproductivity
that the the laser spotof LALsize,
can bethe scanning
increased speed (relative
by reducing the spatial movement
between laser beam
overlap and target)
of successive andbythe
laser pulses pulsetherepetition
increasing scanning speed rate tonanosecond-pulsed,
in the avoid shielding caused by the
IR laser
ablation of Al O
previous pulse [82,84,90,91,116].
2 3 in water. The authors achieved full pulse separation, and reached a maximum
productivity at a specific interpulse distance. A linear decrease in productivity at higher distances
Sattari et al. [84] found that the productivity of LAL can be increased by reducing the spatial
overlap of successive laser pulses by increasing the scanning speed in the nanosecond-pulsed, IR
laser ablation of Al2O3 in water. The authors achieved full pulse separation, and reached a maximum
productivity at a specific interpulse distance. A linear decrease in productivity at higher distances
Sattari et al. [84] found that the productivity of LAL can be increased by reducing the spatial
overlap of successive laser pulses by increasing the scanning speed in the nanosecond-pulsed, IR
laser ablation of Al2O3 in water. The authors achieved full pulse separation, and reached a maximum
productivity at a specific interpulse distance. A linear decrease in productivity at higher
Nanomaterials 2020, 10, 2317
distances
15 of 50
followed. Wagener et al. [91] also observed an optimal interpulse distance in the picosecond-pulsed,
Vis laser ablation of zinc in tetrahydrofuran. However, the decrease in productivity at longer
followed. Wagener et al. [91] also observed an optimal interpulse distance in the picosecond-pulsed,
interpulse distances without overlap was less pronounced compared to the results of the study of
Vis laser ablation of zinc in tetrahydrofuran. However, the decrease in productivity at longer interpulse
Sattari etdistances
al. [84].without
This was probably
overlap was less due to the compared
pronounced shorter pulse duration
to the results applied
of the study of by Wagener
Sattari et al. [91].
et al. [84].
StreubelThis
et al.
was[44] did not
probably due even observe
to the shorter a decrease
pulse in productivity
duration applied by Wagener at longer
et al. interpulse
[91]. Streubel distances at
et al. [44]
did not even observe a decrease in productivity at longer interpulse distances
an even shorter pulse duration. The thermal heating of the ablation target at longer pulses obviouslyat an even shorter pulse
duration. The thermal heating of the ablation target at longer pulses obviously influences the optimal
influences the optimal interpulse distance.
interpulse distance.
In summary, the productivity in LAL can be optimized by implementing a full spatial pulse
In summary, the productivity in LAL can be optimized by implementing a full spatial pulse
separation. For laser
separation. For pulses longlong
laser pulses enough
enoughtotohave
have aa significant
significant thermal
thermal impactimpact
on theon the ablation
ablation target, target,
the productivity is maximized
the productivity is maximized atatan
anoptimum interpulse
optimum interpulse distance.
distance. FigureFigure 10 illustrates
10 illustrates the effect ofthe
too effect of
too shortshort
andand appropriate interpulse
appropriate interpulse distances on the
distances onproductivity of LAL. of LAL.
the productivity
Figure 10. Illustration

Figure of a too
10. Illustration of a short (a)(a)
too short andandan
anappropriate
appropriate (b)(b) interpulse
interpulse distance
distance in the
in the laser laser ablation
ablation
of metals in liquids. The diagram in (c) demonstrates relative effects of different laser
of metals in liquids. The diagram in (c) demonstrates relative effects of different laser pulse durations pulse durations
on the dependence of the productivity on the inter-pulse distance. In (c), both axes scale linearly.
on the dependence of the productivity on the inter-pulse distance. In (c), both axes scale linearly. The
The trends shown in the diagram represent the interpretation of the combined results of the discussed
trends shown ininthe
literature diagram
Section 2.2.1. Inrepresent
(c), the arrowtheand
interpretation
the less dense of
linethe combined
style indicate theresults
effect ofof the discussed
a longer
literature in pulse
laser Section 2.2.1.onInproductivity.
duration (c), the arrow and the
Reprinted withless dense from
permission line style
[66]. indicate the effect of a longer
laser pulse duration on productivity. Reprinted with permission from [66].
Liquid Environment: The relative motion [117,118], layer height [86,119,120] and physicochemical
nature [66,71,121] of the liquid environment influence the productivity in LAL, as explained in
the following.
A flowing liquid homogenizes the result of LAL compared to a static fluid environment [102,103].
As demonstrated by Streubel et al. [48], the productivity of LAL can be optimized by varying the
flow velocity of the liquid. However, a dilution of the colloid must be accepted in parallel if LAL is
applied continuously. The increase in productivity is probably caused by a faster transport of shielding
species away from the ablation zone and an overall reduction of the concentration of shielding species.
Consequently, the improvement of the productivity must saturate at a specific flow rate.
Interestingly, the height of the liquid layer on top of the ablation target also has an impact on the
productivity. Al-Mamun et al. [86] observed a maximized ablation rate at a minimized layer height
of 2 mm and Jiang et al. [122] found an optimum height at 1.2 mm. Both research groups assumed
a confinement effect as a reason for a generally higher productivity at lower liquid layer heights.
For example, shock waves generated in the ablation process could be reflected back to the target
from the liquid–air interface. In addition, the experimental implementation must also be considered.
Especially for long ablation times and batch setups, the exponential absorption of the laser radiation
by the nanoparticle colloid, described by the Beer–Lambert law, will be much stronger at high liquid
levels. Menéndez-Manjón et al. [44] further pointed out the importance of the compensation of the
change in beam propagation induced by the refraction at the air-liquid interface, when changing the
liquid layer height. The authors also describe the productivity-limiting effect of explosive vaporization
of the liquid at a critical minimum of the liquid layer height. This effect may have led to the optimum
liquid layer height observed by Jiang et al. [119].
The impact of the physicochemical nature of the liquid on the productivity in LAL is more complex.
Baladi and Mamoory [121] investigated the ablation rate in the nanosecond-pulsed, IR laser ablation of
aluminum in ethanol, acetone and EG (ethylene glycol) at comparable laser fluences. They found similar
ablation rates for ethanol and acetone. However, the ablation rate during LAL in EG was lowered by
more than 90%. Cristoforetti et al. [87] observed comparable productivities in the nanosecond-pulsed,
IR laser ablation of palladium in ethanol and 2-propanol, but a productivity reduction in acetone
(by 15%), water (by 20%) and toluene and n-hexane (by 85%). The reasons for those differences in
productivity remained unclear.
Kalus et al. [120] also observed significantly different ablation rates during LAL
(nanosecond-pulsed, IR) in water compared to mono-, di- and tri-EG. The authors could correlate the
reduced productivity to intensified shielding of the laser beam by persistent bubbles. They found
that the size and dwell time of the bubbles depends on the viscosity of the liquid. Consequently,
a higher viscosity promotes shielding and reduces the ablation rate. However, the low-viscous liquid
ethyl acetate did not fit the observed trend. There must be at least one other factor such as the vapor
pressure or the specific heat of vaporization considered to make the shielding by persistent bubbles
more predictive.
Another study on the productivity of LAL in different liquids was conducted by ablating
iron using IR, femtosecond laser pulses. Interestingly, the authors observed an optimum in the
energy-related productivity for all tested liquids (water, methanol, ethanol, acetone and toluene)
at a similar fluence but with different ablation rates. Again, the lowest ablation rate was observed
in toluene, 85% lower than in water. The low applied repetition rate of 1 Hz combined with a low
liquid layer of 4 mm should have minimized shielding effects by persistent bubbles. In addition,
no significant difference was found in the ablation-effective spot diameter and the amount of reflected
laser energy. However, the plasma radiation in different liquids qualitatively mirrored the productivity.
The question for the productivity-lowering liquid parameter remained unanswered, but differences in
the laser penetration depth into the ablation target, as assumed by the authors, were unlikely to take
place at the short pulse duration of 35 fs.
In summary, the productivity of LAL can be improved by applying a liquid flow, by choosing
Nanomaterials 2020,
a low liquid10, xlevel, and by performing LAL in water. In specific cases, water undesirably alters the 16 of 50
properties of the NPs, for instance, by oxidation. Low-viscous organic solvents like ethanol or acetone
represent the best
represent thealternatives ininsuch
best alternatives such aa case.
case.Figure
Figure 11 illustrates
11 illustrates theofeffect
the effect ofvelocity
the flow the flowandvelocity
the and
liquid layer height on the productivity
the liquid layer height on the productivity of LAL. of LAL.
Figure 11. Illustration

Figure of the
11. Illustration effect
of the ofofthe
effect theliquid flowrate
liquid flow rate
(a)(a)
andand
of theof liquid
the liquid layer (b)
layer height height
on the(b) on the
productivity in theinlaser
productivity ablation
the laser of of
ablation metals
metalsinin liquids. Thediagram
liquids. The diagram indemonstrates
in (c) (c) demonstratesrelative relative
effects effects
of different liquid layer heights on the dependence of the productivity
of different liquid layer heights on the dependence of the productivity on the volume flowon the volume flow rate. In (c),
rate. In (c),
both axes scale linearly. The trends shown in the diagram represent the interpretation of the combined
both axes scale linearly. The trends shown in the diagram represent the interpretation of the combined
results of the discussed literature in Section 2.2.1. In (c), the dashed line shows the effect of lower liquid
results of theheight
layer discussed literature in
on the productivity, andSection
the dashed2.2.1.
lineIn (c), the
shows theeffect
dashed line
of a too lowshows the effect
liquid layer height of lower
liquid layer height
compared on solid
to the the productivity,
line, respectively.and the dashed
Reprinted line shows
with permission fromthe effect of a too low liquid layer
[66].
height compared to the solid line, respectively. Reprinted with permission from [66].
Target Geometry: There are three dimensions to vary on the geometry of a bulk ablation target.
By reducing single dimensions of a bulk to sizes comparable to the laser spot, the available target
geometries include foils, wires, and particles. An impact on the ablation rate is discussed below.
Scaramuzza et al. [123] investigated the impact of the dimensional reduction of the ablation
Target Geometry: There are three dimensions to vary on the geometry of a bulk ablation target.
By reducing single dimensions of a bulk to sizes comparable to the laser spot, the available target
geometries include foils, wires, and particles. An impact on the ablation rate is discussed below.
Scaramuzza et al. [123] investigated the impact of the dimensional reduction of the ablation target
on the productivity. The authors found a decrease in the productivity when ablating gold foils with
thicknesses less than 0.1 mm covered with an aqueous saline solution. Nanosecond, IR laser pulses
with a fluence of 4.3 J/cm2 were used. Additionally, debris of gold were present in colloids synthesized
from foils with thicknesses between 100 nm and 0.1 mm, which led to an overestimated ablation rate.
The reduction of another dimension of the ablation target leads to LAL of wires. Messina et al. [124]
achieved ablation rates, which were by a factor of 15 higher compared to a bulk target in the
nanosecond-pulsed laser ablation of silver wires in water at a fluence of 1.5 J/cm2 . An optimal wire
diameter of 0.75 mm existed. The laser beam diameter was 3 mm. A confinement of heat in the wire and
differing cavitation bubble dynamics were named to cause the improved productivity. The method of
how the confinement of heat should affect the wire temperature was calculated by Scaramuzza et al. [123].
The dynamics of the cavitation bubble were investigated by De Giacomo et al. [122] in a comparative
study on bulk and wire ablation.
A recent study of Kohsakowski et al. [90] reported significantly lower differences in LAL of silver
wires and bulk targets. The wire ablation was more productive by a factor of 1.47. This contradictory
result compared to the results of Messina et al. [124] at comparable laser parameters were mainly due
to optimized process parameters in the bulk ablation by Kohsakowski et al. [90].
In conclusion, a higher productivity of LAL can be accessed when ablating macroscopic metal
targets compared to thin foils. However, by laser ablating a wire, the highest productivity in
nanosecond-pulsed metal ablation should be achievable due to heat confinement. An optimal wire
diameter exists, probably in dependence on the laser parameters. Heat confinement in the ablation
target plays a minor role in ultrashort-pulsed laser ablation of metals, making wire ablation probably
less advantageous here. Figure 12 illustrates the described effects of this section.
Figure 12. Illustration of the effect of the target thickness in the laser ablation of metals in liquids (a)
and the influence of the laser pulse duration on the heat confinement in thin targets (b). The diagram in
Figure 12. Illustration of the effect of the target thickness in the laser ablation of metals in liquids (a)
(c) demonstrates relative effects of different laser pulse duration on the dependence of the productivity
and the influence of the laser pulse duration on the heat confinement in thin targets (b). The diagram
on the ablation target thickness. In (c), both axes scale linearly. The trends shown in the diagram
in (c) demonstrates relative effects of different laser pulse duration on the dependence of the
represent the interpretation of the combined results of the discussed literature in Section 2.2.1. In (c),
productivity on the ablation target thickness. In (c), both axes scale linearly. The trends shown in the
the arrow and the less dense line style indicate the effect of longer pulse duration on productivity. In (c),
diagram represent the interpretation of the combined results of the discussed literature in Section
the vertical solid line in the center of the diagram marks the penetration depths of the laser pulse into
2.2.1. In (c), the arrow and the less dense line style indicate the effect of longer pulse duration on
the target material. Reprinted with permission from [66].
productivity. In (c), the vertical solid line in the center of the diagram marks the penetration depths
of the laser
Critical pulse
View oninto the target material.
Possibilities ReprintedImprovement:
of Productivity with permission from [66].
Obviously, the amount
of
productivity-effective process parameters and variables in LAL is extensive and hard to cover due to
Critical View on Possibilities of Productivity Improvement: Obviously, the amount of
the variety and the existing cross-dependencies between the parameters and variables. In addition,
productivity-effective process parameters and variables in LAL is extensive and hard to cover due to
the relevant literature does not provide the data required for a productivity evaluation in a full-range
the variety and the existing cross-dependencies between the parameters and variables. In addition,
parameter variation, not even for a single laser system. Furthermore, important studies like that of
the relevant literature does not provide the data required for a productivity evaluation in a full-range
Riabinina et al. [88] on the impact of the pulse duration on the productivity investigated only one
parameter variation, not even for a single laser system. Furthermore, important studies like that of
material and liquid environment, and neither scanning of the laser beam nor a liquid flow were applied.
Riabinina et al. [88] on the impact of the pulse duration on the productivity investigated only one
material and liquid environment, and neither scanning of the laser beam nor a liquid flow were
applied.
Other important aspects are the limitations given by the equipment and the desired product. In
case specific oxidation states or size distributions of NPs are required, laser ablation probably needs
Other important aspects are the limitations given by the equipment and the desired product.
In case specific oxidation states or size distributions of NPs are required, laser ablation probably needs
to be performed at specific laser parameters and in a particular liquid. Both may lower the ablation rate.
However, there is an optimum set of laser parameters of a specific laser system for each combination of
ablation material and liquid environment. Ideally, this set is evaluated experimentally in each case
productivity plays a major role.
2.3. LAL-Based Techniques for Nanomaterials Synthesis and Processing

In the previous sections, the fundamental mechanisms involved in the LAL process are described
considering the effects of laser parameters, and how the active species act differently in plasma,
cavitation bubbles and droplets as a function of the ablation conditions. We have seen that the
liquid is the second most important parameter after the laser source in LAL. Water and common
organic solvents, including alcohol, acetone and sodium dodecyl sulfate (SDS) have been used
widely in LAL. Moreover, small biomolecules such as aqueous oligonucleotide solutions, polymers,
liquid nitrogen, supercritical carbon dioxide and liquid helium at very low temperatures have been
employed as unique liquids to synthesize nanocrystals and fabricate nanostructures [125].
Recently, important progress to optimize NP production has been also attained following the
introduction of field-assisted LAL. Importantly, the experiments have proven that the morphology,
composition and structure of LAL-generated nanomaterials can be readily controlled by changing
the external environment. Various field-assisted LAL techniques have been developed, such as
temperature field-assisted LAL [126], electric field-assisted laser ablation in liquid (EFLAL) [127],
Magnetic Field-assisted Laser Ablation in Liquid (MFLAL) [128] and electrochemistry-assisted laser
ablation in liquid (ECLAL) [129].
Polyoxometalate (POM) materials, consisting of at least two (usually three or more) transition metal
oxyanions that are linked together by shared oxygen atoms to form a large, closed three-dimensional
framework, were successfully synthesized by ECLAL. POM nanostructures are attractive because
of their high catalytic activity in oil refining, their favorable emission properties and suitability
for energy storage applications [130]. With respect to many other synthesis techniques, ECLAL
advantages are: (i) clean preparation of nanostructures because of its simple starting materials
and limited byproduct formation; (ii) an ambient environment without extreme temperature and
pressure conditions; (iii) flexibility to design various nanostructures by combining specific solid targets,
electrodes and liquids. Liu et al. [131] first prepared POMs by a one-step route using molybdenum as a
solid target, copper as electrodes, and deionized water as the solvent. Two copper electrodes were
placed between the two facing sides of a chamber. A steady electric field with a voltage of 20 V was
produced by a DC power source. The XRD pattern of the as-synthesized nanostructure indicated that
it was a monoclinic phase of crystalline lindgrenite (Cu3 (OH)2 (MoO4 )2 ). No signatures of amorphous
molybdenum, copper compound or any other oxide phase were found in the XRD pattern, indicating
that the synthesized sample is highly pure and crystalline. It emerges that different products should be
obtained combining targets and electrodes of different nature. So, Liang and co-workers used three
different kinds of combinations, vanadium (target) + copper (electrode) [132], vanadium (target) +
silver (electrode) [133] and molybdenum (target) + zinc (electrode) [6], to synthesize ZnMoO4 micro-
and nanoplates and rods, Cu3 (OH)2 V2 O7 ·2H2 O flower-like nanostructures, and Ag2 V4 O11 brush-like
nanostructures. It is worth noticing that in ECLAL, the targets and electrodes used react. This does not
occur in EFLAL.
For instance, Ismail et al. [134] reported the production of Bi2 O3 NPs by the pulsed laser ablation
in water under the effect of the electric field (EFLAL). They found that applying the electric field during
laser ablation led to the increase of the Bi2 O3 particle size. Sapkota et al. [135] used an excimer laser
(351 nm) to ablate a solid tin target immersed in water in the presence of an external electric field,
while Jumaa et al. [136] reported the synthesis of gold NPs by the pulsed Nd:YAG (1064 nm) laser
ablation in deionized water mainly to study the effect of the electric field on the antibacterial activity of
these particles. Al-Haddad et al. [137] synthesized Au NPs by pulsed laser (Nd:YAG, λ = 1064 nm),
ablation of a gold target immersed in deionized water by 300 mJ of laser energy, while a DC electrical
field was applied above the target with adjusted voltage. The influence of the applied electric field on
the formation of platinum NPs by laser (Nd:YAG, λ = 1064 nm) ablation technique was investigated by
Moniri et al. [138]. Furthermore, laser ablation of germanium in liquids with static, externally applied
electric fields is discussed in [139]. The authors found that ablation in water results in spherical NPs
and filaments while ablation in ethanol favors the synthesis of spherical and spindle-shaped NPs.
The latter resulted from ablation only with an electric field strength of 9.5 V/cm, and the target being
immersed in ethanol. A clear correlation between decreasing spherical particle size and increasing
externally applied electric field was found. Similarly, Liu et al. [127], adopting EFLAL, with the second
harmonic of a nanosecond-pulsed, Q-switched Nd:YAG laser-prepared GeO2 micro and nanocubes with
high-index facets and a kind of GeO2 micro and nanospindles. This approach avoids the substantial
quantities of capping agents that are attached to the surface of the GeO2 nanostructures, as observed
on germanium oxide nanomaterials prepared by sol-gel reaction. The synthesis of GeO2 nanocubes
and nanospindles is ascribed to the interaction between the laser beam and the external electric field.
In the process, first the Ge plasma is expected to form because of the high temperature and pressure
induced by laser. Meanwhile, the active O and/or OH species that originate from the decomposition of
water would surround the plasma and react with it to form GeO2 NPs. X-ray diffraction (XRD) and
selected-area electron diffraction (SAED) patterns of the products revealed that the preferred {1011}
plane of GeO2 was dominant. This suggests that the applied electric field helped to stabilize the growth
of {1011} planes, while hindering the growth of planes perpendicular to such planes. In this case, the six
{1011} planes readily formed into the nanocube morphology. As the applied electric field became
stronger, the growth of the {1011} plane would be elongated along the [1] direction, which results in
the formation of spindle-like morphology. Thus, the electric field plays an important role in governing
NP shape.
On the basis of the above-described evidence, it emerges that EFLAL extends the traditional LAL
approach, allowing a better control of the morphology, size, chemical composition and structure of the
metal-based nanostructures as well as an increase of the NP concentration. This is explained taking
into account that: (1) electric field is believed to transport the charged particles produced in the plasma
plume at the electrodes, in a process that resembles electrophoresis; (2) EF allows an efficient removal
of the bubbles formed both in the volume of the liquid and on the target. The delivery of laser pulses
onto the target is more effective and so the ablation rate in liquid is higher by a factor of three (generally,
about 300 mg/30 min) compared to ablation without EF (about 100 mg/30 min).
The EF role on Mo-based nanostructures is also shown by Spadaro and Fazio et al. [140,141]
that deal with the synthesis of Mo oxide nanocolloids using a focused picosecond-pulsed laser beam
(λ = 532 nm, repetition rate = 100 kHz, pulse width = 6–8 ps). A molybdenum target was ablated in
water and the effect of an external EF (the estimated electric field is 20 V/cm, the Pt electrode distance
fixed at 5 cm) applied during the ablation process, has been exploited in order to check for modifications
of the NP surface morphology and surface chemical bonding configurations. The obtained colloids
were sprayed by means of an ultrasonic atomizer on glass substrates to carry out the chemical-physical
characterizations (see Figure 13). A selective tuning of Mo–O chemical bonding configurations and
a suitable control of NP size distributions were achieved by varying the water temperature and
by applying the external EF. Two types of nanocolloids were prepared: one with a spherical shape,
size less than 50 nm and a dominant MoO2 surface chemical configuration, and another with an
oblong structure, where the oxygen deficient MoO3 phase increases at the expense of the MoO2 one.
Both nanocolloids induce metal redox and antioxidant properties which strongly depend on the Mo–O
surface chemical bonding configurations and NP morphology.
Overall, the main interesting evidences are: (i) the possibility of tuning NP surface composition
and surface/volume ratio directly in the production phase, without any post-synthesis treatment,
(ii) the ability to modulate their bio-properties as the production of Reactive Oxygen Species (ROS)
532 nm, repetition rate = 100 kHz, pulse width = 6–8 ps). A molybdenum target was ablated in water
and the effect of an external EF (the estimated electric field is 20 V/cm, the Pt electrode distance fixed
at 5 cm) applied during the ablation process, has been exploited in order to check for modifications
of the NP surface morphology and surface chemical bonding configurations. The obtained colloids
were sprayed
Nanomaterials 2020, 10, by
2317means of an ultrasonic atomizer on glass substrates to carry out the chemical- 20 of 50
physical characterizations (see Figure 13). A selective tuning of Mo–O chemical bonding
configurations and a suitable control of NP size distributions were achieved by varying the water
temperature capability,
and antioxidant and by applying
whichthe external
affect EF. Two types
cell-signaling of nanocolloids
mechanisms. were prepared:
Ultimately, one withto
the possibility a tune
spherical shape,
the properties size lessnanostructures
of Mo-based than 50 nm and is atodominant MoO2 useful
be considered surfacefor
chemical
future configuration, and
innovative biomedical
another with an oblong structure, where the oxygen deficient MoO3 phase increases at the expense
applications to identify potential anticancer complexes acting through ROS production or redox
of the MoO2 one. Both nanocolloids induce metal redox and antioxidant properties which strongly
dependent mechanisms.
depend on the Mo–O surface chemical bonding configurations and NP morphology.
Figure 13. Schematic of LAL (a) and EFLAL setups (b); ultrasonic atomizer setup (c).
Figure 13. Schematic of LAL (a) and EFLAL setups (b); ultrasonic atomizer setup (c).
Overall, the main interesting evidences are: (i) the possibility of tuning NP surface composition
In the next sections, we draw the reader’s attention to a report with specific details on promising
and surface/volume ratio directly in the production phase, without any post-synthesis treatment, (ii)
applications of LAL nanostructures (mainly plasmonic metal-based NPs) for biotechnology applications
the ability to modulate their bio-properties as the production of Reactive Oxygen Species (ROS) and
and for organic capability,
antioxidant pollutantswhich
degradation. Remarkably,
affect cell-signaling these fields
mechanisms. were not
Ultimately, thecovered, to to
possibility the best
tune theof our
knowledge, in previous reviews that were mostly dedicated to catalysis.
properties of Mo-based nanostructures is to be considered useful for future innovative biomedical
In addition,to
applications based on our
identify interactions
potential anticancerwith industrial
complexes partners
acting andROS
through pharmaceutical
production orcompanies,
redox
at present we believe
dependent that the main difficulty is cultural. The technicians of these companies are mainly
mechanisms.
chemists In
bythe next sections,
training, we draw the
and therefore havereader’s attentionfor
a preference to achemical
report with specific details
techniques on promising
that they feel closer to
applications of LAL nanostructures (mainly plasmonic
their culture. A simple explanation, but a difficult barrier to overcome.metal-based NPs) for biotechnology
applications and for organic pollutants degradation. Remarkably, these fields were not covered, to
the best ofApplications
3. Promising our knowledge,
ofinLAL
previous reviews that were
Nanostructures mostly dedicated
for Biotechnology to catalysis. and for
Applications
In addition, Degradation
Organic Pollutants based on our interactions with industrial partners and pharmaceutical companies,
at present we believe that the main difficulty is cultural. The technicians of these companies are
3.1. Plasmonic Properties
mainly chemists of Metaland
by training, Nanoparticles and aPlasmon
therefore have Sensitivity
preference for chemical techniques that they feel
closer to their culture. A simple explanation, but a difficult barrier to overcome.
Plasmonics involves the control of light at the nanoscale by using surface plasmons. Localized
surface plasmon resonance (LSPR), which imparts unique optical properties to metal nanostructures,
involves the collective and coherent oscillation of dielectrically confined conduction electrons on the
surface of metal nanostructures under the effect of electromagnetic fields [142,143].
Owing to the unique combination of physical and chemical properties, such as large absorption
and scattering cross-section, high sensitivity to local dielectric environment and enhanced electric
field at the surface, plasmonic nanostructures are emerging as an important class of materials for
various optical sensing applications. Plasmonic systems in particular have been studied extensively
due to their ability to confine light below the diffraction limit, which greatly enhances their sensitivity
compared to conventional approaches [144]. The oscillating electric field of an electromagnetic wave
causes the formation of dipoles and multipoles in metallic NPs. Such multipoles depend on the size
and shape of the NP in a way predictable by solving the Maxwell equations at the interface between
the metal and the external medium. For noble metals, the plasmonic response of the NP falls into
the UV-vis-NIR frequency range and it is significantly observed by considering the absorption and
scattering cross sections. In a classical transmittance experiment the overall extinction effect (the sum
of scattering and absorption) can be measured. If we restrict our consideration to a spherical NP with a
size much smaller so that the impinging radiation wavelength scattering can be neglected (quasi static
approximation) and a simple dipole is sufficient to account for the plasmonic behavior:
µ = αE (10)
where α is the electric polarizability and E is the electric field. In this case the polarizability is
expressed as:
ε − εm
α = 4πε0 R3 (11)
ε + 2εm
where ε is the dielectric function [ε1 (ω) + iε2 (ω)] and R the radius of the NP. The resonance condition
is achieved for maximum polarizability, which happens for ε = −2εm . It is thus clear that plasmon
resonance depends on the metal through its size and dielectric function and on the medium through its
dielectric constant εm (and thus the refractive index n). Much more complex is the situation in all those
cases where the NP has a shape far from spherical-like and proper simulations about the plasmonic
response should be conducted to interpret the response [142,144,145].
Laser ablation of metallic targets permits the formation of noble metal NPs in a range of solvents,
including water and alcohols. Among noble metals, gold has been the most intensely studied, followed
by silver. Both NPs can be produced as stable suspensions by LAL with diameters in the range
10–30 nm. Being different metals, they have different dielectric functions allowing plasmon resonances
in different spectral regions. Indeed, Ag NPs have their typical plasmon resonance just below
400 nm, which instead lies around 510–530 nm for Au NPs. Despite plasmon resonance depending
on particle size, a tuning across a broad range of the spectrum is not achievable just by adjusting
spherical particle size. One way to overcome the issue is by alloying [145,146]. Figure 14a shows that
even Au/Ag colloidal NP alloys can be grown if the ablation is performed using an alloy target in
water [147]. Here, we refer to a gold 70% molar concentration with respect to silver, but any result can
be obtained by tuning the concentration, thanks to the total miscibility of the two metals. This ensures
the possibility to tune the plasmon resonance from that of silver (400 nm) to that of gold (520 nm)
continuously, opening the way to a fine plasmonic response. Alternatively, a very similar result can be
obtained by pulsed laser irradiation of a previously formed Au/Ag colloidal mixture [147]. While in
the former case the plasmon resonance tuning can be achieved only by choosing a different alloy target
for every composition, in the latter case, the colloidal mixture can be prepared in any metal ratio from
pure metal colloids, which is a clear advantage. Figure 14b reports a range of simulations conducted
using a Boundary Element Method (BEM) developed by A. Trügler [148]. In this case a dielectric
environment (water) where bodies with homogeneous and isotropic dielectric functions are separated
by abrupt interfaces is assumed, thus solving Maxwell equations using the boundary conditions at the
particle boundaries. As for the dielectric function of the considered Au/Ag alloy, a weighted average
method was used, in which the dielectric function of the alloy is defined as:
εalloy (ω) = x εAu (ω) + (1 − x) εAg (ω) (12)
where x denotes the Au molar fraction in the Au−Ag alloy [149].

The simulation results shown in Figure 14b agree with the experimental results concerning the
plasmon resonance position. The smaller width of the simulated extinction spectra is attributed to the
difficulty to set an appropriate damping constant. The same BEM method predicts that as an Au NP
grows larger, the plasmon resonance slightly red-shifts and broadens. However, in order to be able to
tune the plasmon resonance of a metallic NP, playing with the size is not enough to explore a broad
range [143,150]. It has to be noted that Equation (1) is strictly valid only for spherical particles, while for
particles with different shapes, the geometry must be taken into account and a plasmon resonance
shift can be expected. Indeed, beside the aforementioned alloying, a shape change is another effective
strategy to tune the plasmon resonance. This was observed experimentally in gold nanorods [151,152],
gold nanostars [153] and silver nanoplates [154,155].
As an example, Figure 15a shows how the typical plasmon resonance observed around 400 nm for
spherical Ag NPs is red-shifted to around 600 nm as the particles are transformed to flat triangular
nanoplates. Spherical NPs were obtained by LAL in water with citrate as capping agent, using a
1064 Nd:YAG-pulsed laser. These show a single plasmon resonance feature at 393 nm, indicating
particles in the region of 10 nm, as can also be observed by SEM in Figure 15b. When such particles
are irradiated with white light, in association with H2 O2 addition, a dramatic spectral change occurs,
with the formation of two main features [156]. One feature is red-shifted to ~600 nm and represents the
longitudinal in-plane dipole mode [157]. The other important feature, despite its low intensity, is the
out-of-plane quadrupole mode, at 335 nm, which is an indication of anisotropy in the structures [157].
Indeed, spherical particles are converted into flat triangular ones, sized around 100 nm and thick about
10–20 nm, as shown by scanning electron microscopy images and atomic force microscopy profiles in
Figure 15c,d.
Such transformation is typically achieved using a process named “seed-mediated growth”,
which involves the chemical synthesis of Ag NPs starting from an Ag+ salt and reducing agents
as a first step, followed by a further chemical process to transform initial spherical particles,
or “seeds”, into triangular nanoplates [158–160]. However, the use of LAL for the production of
the seeds, coupled with light irradiation and H2 O2 addition, has the great advantage of being an
environment-friendly process that does not involve the use of strong reducing agents or harmful
chemicals [156,161,162]. Moreover, LAL is a very versatile tool where virtually any material can be
produced in any liquid without any other chemical involved. This allows for a wide freedom in
the use of a variety of capping agents which can be chosen depending on the final application or
process needs. Indeed, citrate is an excellent example as, within the process described above, it is used
as both a capping agent to stabilize the particles in water, as a driver for growth and reshaping and as
a mild reducing agent. The above mentioned dependence of the plasmon resonance on the refractive
index of the medium can be exploited for optical sensing applications [163], even at a single molecule
level [164,165], as it allows the detection of molecules dissolved in the colloidal phase or adsorbed on
the surface, as long
Nanomaterials as10,they
2020, x cause a variation of the refractive index of the medium [166,167]. 21 of The
50 key
property is the variation of the plasmon resonance relative to the refractive index change, or plasmon
simulations conducted using a Boundary Element Method (BEM) developed by A. Trügler [148]. In
sensitivity, which can thus be defined as:
this case a dielectric environment (water) where bodies with homogeneous and isotropic dielectric
∆λ
functions are separated by abrupt interfacesSis= assumed, thus solving Maxwell equations using the (13)
boundary conditions at the particle boundaries. As∆n for the dielectric function of the considered Au/Ag
where ∆λ is athe
alloy, plasmon
weighted resonance
average method wasvariation
used, in in wavelength
which associated
the dielectric function of to
thethe
alloyrefractive
is defined index
variation ∆n. S is typically expressed in terms of nm/refractive index unit (RIU). S can be easily
as:
measured by performing a relatively simple εalloy(ω) experiment
= x εAu(ω) + (1in which
− x) εAg(ω)a small aliquot of colloid (12) solution is
mixed with a sucrose solution at a set concentration, in
where x denotes the Au molar fraction in the Au−Ag alloy [149].
a 20–70% range, where a direct relationship
between sucrose concentration and refractive index exists [168].
Figure 14. Absorption

Figure spectra
14. Absorption of Ag,
spectra Ag:Au
of Ag, Ag:Au and AgNP
and Ag NPcolloids
colloids produced
produced from:from: (a)ablation
(a) laser laser ablation
in
liquids
in liquids of Ag,
of Ag, Ag:Au alloy
Ag:Au alloy and
andAuAu targets, respectively;
targets, (b) a Boundary
respectively; Element Method
(b) a Boundary Element (BEM)Method
simulation.
(BEM) simulation.
The simulation results shown in Figure 14b agree with the experimental results concerning the
plasmon resonance position. The smaller width of the simulated extinction spectra is attributed to
the difficulty to set an appropriate damping constant. The same BEM method predicts that as an Au
NP grows larger, the plasmon resonance slightly red-shifts and broadens. However, in order to be
able to tune the plasmon resonance of a metallic NP, playing with the size is not enough to explore a
15. Optical absorption spectra of spherical vs triangular silver NPs (a); SEM image of spherical
FigureFigure
15. Optical absorption spectra of spherical vs triangular silver NPs (a); SEM image of spherical
NPs (b) and of triangular nanoparticles (c) TEM image and in the inset AFM profiles of triangular NPs
NPs (b) and of triangular nanoparticles (c) TEM image and in the inset AFM profiles of triangular
(d). Reprinted from Ref. [156], Copyright (2019), with permission from Elsevier.
NPs (d). Reprinted from Ref. [156], Copyright (2019), with permission from Elsevier.
Figure 16a shows an example of plasmon sensitivity measurements for Au and Ag spherical NPs
Such transformation
produced is typically
by LAL in water. Ag NPs showachieved
higher using a process
sensitivity named than
(125 nm/RIU) “seed-mediated growth”,
Au NPs (45 nm/RIU)
whichand involves the
are thus chemical
more widelysynthesis
investigatedof for
Ag these
NPs type
starting from an AgHowever,
of applications. + salt andwhen
reducing agents
spherical NPsas a
are converted into nanoplates, the plasmon sensitivity shows a roughly threefold
first step, followed by a further chemical process to transform initial spherical particles, or “seeds”, increase [161,169],
as shown innanoplates
into triangular Figure 16a. Plasmon
[158–160].sensitivity
However, can be further
the use of increased
LAL for if thetheAgproduction
NP colloid isofirradiated
the seeds,
with monochromatic light instead of white light [170]. Indeed, irradiating
coupled with light irradiation and H2O2 addition, has the great advantage of being an environment- at 730 nm causes the
formation of particles with S = 460 nm/RIU [170] (Figure 16b). On the other hand, other irradiation
friendly process that does not involve the use of strong reducing agents or harmful chemicals
wavelengths yield NPs with lower sensitivity, hence the wavelength of choice appears a key factor in
[156,161,162]. Moreover, LAL is a very versatile tool where virtually any material can be produced in
enhancing plasmon sensitivity.
any liquid without any other chemical involved. This allows for a wide freedom in the use of a variety
This plasmon sensitivity behavior has the potential for the development of sensing systems where
of capping agentsofwhich
the presence can in
an analyte besolution
chosencould
depending on the
be detected final application
by simple or processprovided
optical measurements, needs. Indeed,
they
citrateinduce
is an excellent
a change inexample as, within
the refractive index.the processindescribed
Selectivity above, aitchallenge
this case remains is used as
thatboth a capping
researchers
agent have
to stabilize
to solve,the
forparticles in water,
example through as a driver
specific for growthofand
functionalization the reshaping
NPs. and as a mild reducing
agent. The above mentioned dependence of the plasmon resonance on the refractive index of the
medium can be exploited for optical sensing applications [163], even at a single molecule level
[164,165], as it allows the detection of molecules dissolved in the colloidal phase or adsorbed on the
surface, as long as they cause a variation of the refractive index of the medium [166,167]. The key
property is the variation of the plasmon resonance relative to the refractive index change, or plasmon
sensitivity, which can thus be defined as:
∆𝜆
𝑆= (13)
Δ𝑛
are converted into nanoplates, the plasmon sensitivity shows a roughly threefold increase [161,169],
as shown in Figure 16a. Plasmon sensitivity can be further increased if the Ag NP colloid is irradiated
with monochromatic light instead of white light [170]. Indeed, irradiating at 730 nm causes the
formation of particles with S = 460 nm/RIU [170] (Figure 16b). On the other hand, other irradiation
wavelengths yield NPs with lower sensitivity, hence the wavelength of choice appears a key factor
in enhancing plasmon sensitivity.
Figure 16. Plasmon sensitivity measurements from gold and silver spherical nanoparticles, obtained
Figure 16. Plasmon sensitivity measurements from gold and silver spherical nanoparticles, obtained
by laser ablation in water, and silver triangular nanoplates obtained by white light irradiation of
by laser ablation in water, and silver triangular nanoplates obtained by white light irradiation of the
the same spherical NPs (a); plasmon sensitivity measurements from triangular NPs obtained from
same spherical NPs (a); plasmon sensitivity measurements from triangular NPs obtained from
monochromatic light irradiation of spherical NPs (also shown) obtained by laser ablation (b). Figure 16a
monochromatic light irradiation of spherical NPs (also shown) obtained by laser ablation (b). Figure
reprinted from Ref. [156], Copyright (2019), with permission from Elsevier. Figure 16b reprinted from
16a reprinted from Ref. [156], Copyright (2019), with permission from Elsevier. Figure 16b reprinted
Ref. [170], with the permission of The Royal Society of Chemistry.
from Ref. [170], with the permission of The Royal Society of Chemistry.
3.2. Plasmonic Nanocolloids for Biotechnology Applications
This plasmon sensitivity behavior has the potential for the development of sensing systems
whereColloidal solutions
the presence of anof plasmonic
analyte in NPs synthesized
solution could beby laser ablation
detected by simplein solution (LAL) are key
optical measurements,
materials
provided for
theybiotechnology
induce a change applications. We index.
in the refractive discuss some ofinour
Selectivity thiscontributions
case remains atochallenge
recall such
that
applications. NPs are synthesized without stabilizing molecules, in
researchers have to solve, for example through specific functionalization of the NPs.order to avoid any associated
biocompatibility problem. Furthermore, the naked surface of these NPs can be easily functionalized,
for
3.2.example with
Plasmonic moleculesforfor
Nanocolloids active cell targeting
Biotechnology [171–173], for sensing and diagnosis [174–176],
Applications
for drug monitoring [177] and also for therapies, as in the case of photothermal therapy [171,175].
UsingColloidal
multiple solutions of plasmonic
functionalizations, NPs synthesized
theranostic nanosystems,by laser ablation
namely in solution
nanosystems (LAL)for
useful are key
both
materials
therapy andfor biotechnology
diagnosis, can alsoapplications.
be obtained. We discuss some of our contributions to recall such
applications. NPs are synthesized
Thanks to their chemical stability withoutgoldstabilizing molecules,
nanoparticles (AuNPs)in order to avoid
are very any associated
frequently used in
biocompatibility problem. Furthermore, the naked surface of these NPs can be easily
comparison to other metallic NPs, such as Ag NPs, which cause toxic effects due to ion solubilization. functionalized,
for presence
The example with molecules
of localized for active
surface plasmonscell (LSPs)
targeting [171–173],
is an for property
interesting sensing and diagnosis
of this type of [174–176],
NPs that
for drug monitoring [177] and also for therapies, as in the case of photothermal
can be exploited for many applications. LSPs arise from collective oscillations of the free electrons therapy [171,175].
of
Using multiple functionalizations, theranostic nanosystems, namely nanosystems
metal nanoparticles and show resonances in the visible and near infrared spectral range, depending useful for both
therapy
on shape,and diagnosis,
dimensions andcan also be obtained.
aggregation of the nanostructures, with very large extinction cross sections
Thanks to their chemical stability
if compared to organic dyes [154]. LSP resonances gold nanoparticles
(LSPR) depend (AuNPs)
also are very
on the frequently
particle used in
surrounding
comparison
(in particular to
byother metallic index)
its refractive NPs, suchandas Ag NPs,
sensors canwhich cause toxic
be developed on effects
such a due to ion solubilization.
dependence. Moreover,
excitation of the LSPR amplifies the incoming electromagnetic field at the NP surface by some orders
of magnitudes within a few nm [178]. This amplification made possible the exploitation of Raman
spectroscopy in the field of sensing technology with the technique called Surface Enhanced Raman
Scattering (SERS). In this case, for molecules near the surface of plasmonic NPs, one can obtain
amplifications of the vibrational Raman spectrum of up to 10 orders of magnitude and even more in
favorable conditions [178].
NPs synthesized by LAL are of particular interest because of their clean surface, which allows
functional molecules to reach easily the NP surface [179,180]. Antigen cell targeting [171–173,180–182],
direct or indirect analytical sensors [177,179,183] and multimodal contrast agent in vivo [182]
are examples of recent results obtained in our laboratories with plasmonic nanostructures for
biotechnology applications.
The identification of antigens expressed by cells allows active targeting of individual cells,
which is relevant in the early stage recognition of cancer cells. We developed a methodology for
detecting cancer cells based on sub-nanomolar concentration of nanocolloids functionalized with
monoclonal antibodies [147,148] or with engineered targeting peptides [172,180–183]. SERS labels,
namely molecules showing huge SERS signals when coupled to plasmonic NPs, were used on the
nanostructures to identify active targeting events using the presence of SERS signals on individual cells
incubated with the nanostructures. SERS signals are vibrational signals, which are easily recognized
and cannot be confused with other signals, like in the case of fluorescent signals usually exploited
for this purpose. Our protocol is efficient because the naked particles, synthesized by laser ablation,
are functionalized simply by mixing the colloidal solution of Au NPs with the solutions of the targeting
molecules, without the need to control the exchange with stabilizing molecules used in other NP
preparations. Molecules and also antibodies are thiolated to assure a strong link with the Au NPs.
Strong SERS signals are obtained by controlling the aggregations of NPs, which create the hot spots
where molecules show very intense SERS signals.
Incubations of the functionalized nanostructures were obtained with cancer cells overexpressing,
or not, the target antigen. For the active targeting of prostatic cancer cells, nanostructures functionalized
with antibodies for prostatic specific membrane antigen (PSMA) and prostate stem cell antigen (PSCA)
antigens were considered [178,180]. Sensitivity (correct targeting among positive cells) and specificity
(absence of targeting among negative cells) of the order of 90% were obtained showing the efficiency of
the prepared nanostructures [180].
Monoclonal antibodies can be, however, immunogenic and usually their cost is very high. Small
molecules like peptides are targeting units that do not show the problem of immunogenicity and their
cost is much lower. In this case, however, the affinity for specific antigens is low. We have prepared
nanostructures with the following peptides: GE11, which targets epidermal growth factor receptors
(EGFRs) expressed in different types of tumors [172,181], RGD for v3 integrin, an adhesion receptor
found in tumors at metastatic level [182], targeting and PreS1 for SerpinB3, a protein overexpressed by
liver tumor cells, targeting [180].
The results show the need to engineer the peptides for the NP functionalization. A long
polyethylene glycol (PEG) chain (3000 molecular weight) and a short-charged lysine sequence linked to
the active peptide are required to obtain high targeting efficiencies that, in particular for specificity, are
found to be also better than those obtained with a specific monoclonal antibody already used in clinic.
The results suggest that the large number of peptides (thousands per particle) per NP overcome the
problem of the small affinity of the single peptide, exploiting the avidity of an ensemble of targeting
units on a single nanostructure. With this approach, sensitivity and specificity larger than 80–90% are
obtained [171,182] (see Figure 17a). Models for the arrangement of the targeting units on the Au NP
surface, obtained with Molecular Dynamics calculations, show that the presence of the short lysine
charged sequence is strategic for obtaining the appropriate exposition of the targeting peptide over the
PEG chains, collapsed over the NP surface [172,182].
SERS signals, as a new approach for the detection of targeting events are much more efficient than
the usual fluorescence signals and allow very easy multiplexing measurements because of the very
narrow bands that can be recorded for vibrational SERS spectra with respect to the very large bands
observed for fluorescence spectra [175]. SERS signals are particularly useful when used for in vivo
studies where autofluorescence of tissue and other biological components hamper the detection of
low intensity fluorescence signals. This is not the problem of SERS signals in particular when they
derive from SERS labels with known spectra. After inoculation of nanostructures with SERS signals
into mice, we were able to easily find SERS signals in their organs where nanostructures accumulated,
or in a tumor, whose margins can be easily obtained with SERS signals. An example is the targeting
of SerpinB3 antigen, expressed by liver tumor cells in a mouse which overexpressed this protein,
using nanostructures functionalized with the peptide PreS1. The targeting activity was first evidenced
in in vitro studies and, when applied to animal trials, the targeted organs reported bright SERS signals
with a complete
Nanomaterials clearance
2020, 10, x in 6 h [180]. Another example was obtained with nanostructures constructed 25 of 50
as multimodal contrast agents. In particular we obtained a nanostructured system in which a SERS
the and
label Au NP
an MRIsurface, obtained
contrast agentwith
based Molecular
on Gd3+ Dynamics calculations,
were present. MRI imagesshow
of athat the were
tumor presence of the
obtained
forshort
micelysine
injectedcharged
with thesequence is strategic
nanostructures for obtaining
together with SERSthe appropriate
images, exposition
which easily showedof the
the targeting
margin
ofpeptide over
the tumor the (see
[182] PEGFigure
chains,17b).
collapsed over the NP surface [172,182].
Figure
Figure 17.17. Nanoparticlesobtained
Nanoparticles obtainedbybyLAL
LAL are
are particularly
particularly versatileforfor
versatile biotechnologyapplications.
biotechnology applications.
(a)(a) active
active antigen
antigen targeting
targeting ofof cells
cells overexpressing
overexpressing oror not
not the
the antigen
antigen using
using Surface
Surface Enhanced
Enhanced Raman
Raman
Scattering
Scattering (SERS)
(SERS) signals;
signals; (b) multimodal
(b) multimodal contrastcontrast
agents andagents and hyperthermal
hyperthermal experiments;experiments;
(c) therapeutic(c)
therapeutic
drug monitoringdrug monitoring
with with aSERS
a competitive competitive
protocol.SERS protocol.
These
SERSexperiments
signals, as a also
newmadeapproach it possible
for the to use NPsoffor
detection photothermal
targeting events are therapy
muchofmore the tumor,
efficient
evidencing
than the usual an increase of thesignals
fluorescence tumorand far allow
field measured
very easy temperature, after 10 min ofbecause
multiplexing measurements irradiation,
of the
byvery narrowwhich
8 degrees bandsisthat can be recorded
considered sufficient fortovibrational SERS spectra
start the apoptosis with respect
mechanism to the
for the tumorverycells.
large
Inbands
vitro experiments also showed that few minutes of irradiation allowed
observed for fluorescence spectra [175]. SERS signals are particularly useful when used for killing about 98% ofin
irradiated
vivo studies cells,where
whichautofluorescence
were targeted byofthe functionalized
tissue NPs [171].components hamper the detection
and other biological
SERS
of low signalsfluorescence
intensity are usually signals.
considered Thisnot appropriate
is not the problem forofquantitative
SERS signalsevaluations
in particular because
when they of
derive from
uncertainty SERS
in the labels with known
reproducibility spectra.
of the SERS After with
substrate inoculation
the presentof nanostructures
hot spots. We have withparticipated
SERS signals
ininto
a verymice,recent collaboration,
we were able to easilyin find
which NPs,
SERS produced
signals in theirbyorgans
laser ablation at our lab, were
where nanostructures tested in
accumulated,
15orlaboratories
in a tumor,aroundwhose margins
Europe in cananbeexperiment
easily obtained with SERS
coordinated by signals. An example
the University is thewithin
of Trieste targetinga
of SerpinB3
COST antigen, expressed
action (Raman4clinics). The by liverwere
results tumor cells
very in a mouse
satisfactory andwhich overexpressed
show that, in particular this protein,
with the
Auusing
NPs, nanostructures
a linear relationshipfunctionalized
between signals withand the peptide
analyte PreS1. The
concentration wastargeting
obtained withactivity was first
appropriate
evidenced in in
reproducibility vitro
and studies
trueness and, when applied to animal trials, the targeted organs reported bright
[179].
SERS signals with
Furthermore, we afound
complete
that aclearance
quantitative in 6approach
h [180].can Another example
be obtained in anwas obtained like
application with
nanostructures
Therapeutic constructed
drug monitoring (TDM)as also
multimodal
with drugscontrastspiked inagents.
plasma, In which particular
simulateswe a realobtained
situation. a
nanostructured
Plasma system
is a difficult in which
matrix due to a SERS label and
the large an MRI contrast
concentration agent based
of proteins, which oninterfere
Gd3+ were withpresent.
the
MRI images
availability of of
hota spots
tumorofwere obtained for mice
the nanostructures forinjected
the SERS with the nanostructures
spectra. together
It is worth to recall the with SERS
protocol
images,
used for thewhich
TDMeasily
in theshowed the margin
case of Erlotinib, of the tumor
a therapeutic [182]
drug for(see Figure
cancer cells17b).
overexpressing EGFR [153].
A SERSThese experiments
measurement also that
requires made theit molecule
possible to be userevealed
NPs forshows photothermal
strong SERS therapy of the
signals, whichtumor,
is
evidencing
usually an increase
observed when a of the tumor
resonance of far
the field measured
exciting temperature,
laser line after 10 min
with the molecular of irradiation,
excitations by 8
is present,
degrees the
obtaining which is considered
so-called sufficient to
surface enhanced start the
resonant apoptosis
Raman mechanism
scattering (SERRS). forSince
the tumor
this iscells. In vitro
not always
experiments
possible for thealso showed that
molecules to befew minuteswe
revealed, of irradiation
found thatallowed killing approach
a competitive about 98%isofmore irradiated cells,
efficient.
which
This were
is the casetargeted by the functionalized
of the Erlotinib molecule, which NPsabsorbs
[171]. in the UV spectral region, far from the laser
SERSinsignals
excitations are usually
the visible, considered
or near infrared not appropriate
spectral region where forthe
quantitative
LSPR lie. Inevaluations because of
this case, a molecule
uncertainty
with strong SERRS in the reproducibility
signals of the SERS
is used, in competition withsubstrate
the molecule with tothebe present
revealed,hot for spots. We have
the occupation
ofparticipated
the hot spots inof
a very recent collaboration,
the nanostructures. in whichwe
The protocol NPs,
used produced
favoredby thelaser ablation
coupling at our
of the lab, were
molecules
tested
with thein 15 laboratories
gold nanostructures around
withEurope in an experiment
a click reaction coordinated
for both Erlotinib andby thethe Universitymolecule.
competitor of Trieste
within a COST action (Raman4clinics). The results were very satisfactory and show that, in particular
with the Au NPs, a linear relationship between signals and analyte concentration was obtained with
appropriate reproducibility and trueness [179].
With this approach the sensibility increased for low concentration of the drug because the signals of
the competitor were high (see Figure 17c). The statistics intrinsic in a large number of hot spots made
the protocol appropriate for quantitative results, as it was shown. Additionally, for this application
naked particles like those obtained by the LAL are important because of their easy functionalization.
As a final remark, one can recall that NPs obtained by laser ablation are very useful in particular
when they have to be functionalized, as it is needed for biotechnology applications, and SERS signals
are used as signals for detection and diagnosis.
3.3. Metal Oxide Nanostructures for UV-SERS Sensing Applications

Traditionally, nanoplasmonics focuses on noble metals (Au, Ag, Cu) or their alloys whose
LSPRs are in the visible (Vis) or near-infrared (NIR) spectral regions [184]. In the ultraviolet
(UV) region the considerable damping due to interband transitions [185] make electromagnetic
enhancements comparatively small. Nevertheless, UV nanoplasmonics may offer new opportunities
in surface-enhanced Raman spectroscopy (SERS) [186], photocatalysis [187], biology [188] and public
safety and security for the detection of organic molecules and hazardous organic compounds [189].
Such molecules show strong electronic absorption in the UV region, which may trigger the resonant
Raman (RR) effect under UV excitation. The RR effect leads to ca. 108 -fold enhancement of the Raman
cross-section, allowing to detect ultralow molecular concentrations [190].
Theoretical studies predict that metals with a large negative real part and a small imaginary part
of the dielectric constant in the UV are suitable candidates for UV-SERS [191]. The most experimentally
tested UV-SERS platforms are Al, Ga, In, Pb, Sn, Bi, Rh, Ru, Pt and Pd, owing to their availability
and to the absence of interband transitions in the UV [192]. For instance, an ultrasensitive label-free
detection of adenine molecules adsorbed on Al nanoparticle arrays using deep-UV SERS (with 257.2 nm
excitation) was reported [193]. However, similar to Mg, Al suffers from the formation of an oxide layer
several nanometers thick that limits the UV plasmonic performance. Although encapsulating the metal
core within chemically inert ultrathin silica shells is a strategy to overcome this issue, it is difficult to
implement given the not-easy-to-control thickness of the SiO2 shell [194–196]. Ga is interesting for its
self-terminating oxide monolayer, but it has an intrinsic low electrical conductivity besides the melting
point near room temperature that hinders its manipulation [197,198]. Interestingly, Bi NPs prepared by
laser ablation in solution [199] display LSPRs from the near UV to the IR absorption region. By using
such Bi NPs as a SERS platform, the spectra of several amino acids were obtained [199], thus indicating
that Bi could be considered an interesting material for the SERS detection of biomolecules, a task that
is usually pursued by means of Ag and Au nanostructures. We outline that Bi plasmons lie in the
UV region, whereas the Raman experiments were carried out with visible lasers [199], namely in
correspondence of the tail of the optical absorption curve. Therefore, it is not possible to fully assess
whether the Raman enhancement is purely electromagnetic, or chemical.
Among the transition metals, Rh has been recently discovered as a novel, nonoxidizing plasmonic
contrast agent, exhibiting UV plasmonic behavior in the region between 3 eV and 7 eV, with the
advantages of its oxide-free nature [200]. Despite theoretical indications, just a few papers reported
UV SERS experiments with Rh based materials; we list them below, to the best of our knowledge at the
time of the present writing:
• The first SERS report is due to Bilmes et al. [201] who observed an increased pyridine Raman
activity on an electrochemically roughened Rh substrate. The observed enhancement was very
low because visible radiation was employed as the exciting source (far from the wavelength of the
Rh SPR absorption peak);
• Lin et al. [202] reported UV-SERS on Rh nanostructured surfaces, and estimated the enhancement
factor to be about 102;
• Zettsu et al. [203] published high-quality UV-SERS spectra (under 325 nm excitation) of
4-mercaptopyridine attached to sub-10 nm tripod-shaped stars of Rh;
• Watson et al. [204] reported a comparative study employing Rh tripod geometry by means of
SERS, surface enhanced fluorescence (SEF) and photo-induced degradation of p-aminothiophenol
(PATP) under UV and visible excitation;
• Ren et al. [205] demonstrated SERS enhancement for pyridine adsorbed on roughened Rh and Ru
electrodes with 325 nm excitation;
• Li et al. [206] reported on amorphous rhodium sulfide microbowls, which were successfully
designed and synthesized with the guidance of theoretical calculations and characterized by an
excellent SERS performance. The amorphous structure favors efficient interfacial charge transfer,
and the bowl-like shape is beneficial for photon trapping by multiple light scattering.
To date, the Rh nanostructures investigated were grown by electrochemical roughening of Rh

surfaces [207] or by chemical methods using different Rh precursors [208]. The limited number
of papers on UV-SERS is mainly because the application of deep-UV excitation very often leads
to photo-degradation of the samples. The availability of a consistent SERS enhancement in the
deep-UV spectral region would therefore allow recording Raman spectra with very low excitation
power [190,209], which would be beneficial to reduce photo-degradation issues.
In the recent past, pulsed laser ablation was used to make planar homogeneous Rh thin films
with thickness up to 1 µm for the realization of mirrors to be used in harsh environments [210,211].
Under proper experimental conditions, LAL allows for the production of colloidal Rh suspensions in a
suitable liquid medium [212–214], which can be employed for the fabrication of nanostructured Rh
substrates with SPR peak in the 250–320 nm region. These LAL-synthesized Rh NPs are almost spherical,
and their size and density distributions are markedly affected by the liquid (water, or ethanol) selected
for LAL: Rh NPs obtained in water are smaller than those obtained in ethanol. The extinction spectra of
the two colloids show the contribution associated to the SPR of the Rh NPs below 400 nm but, for the
samples prepared in ethanol, an additional absorption feature is observed around 340 nm, which may
be ascribed to Rh-C bonds [215]. The size of the NPs is affected by the chemical interactions that occur
during the ablation process, in turn determined by the liquid environment. As discussed in [212],
XRD and XPS results show that ablation of Rh in water leads to the production of mixed Rh/Rh-oxide
phases (RhO2 and Rh2 O3 ), whereas in ethanol essentially metallic Rh NPs are produced, in agreement
with [216].
By fabricating a simple conductometric platform with Rh NPs produced by LAL in water,
Fazio et al. [212] have demonstrated the sensing properties of Rh nanostructures toward low
concentration of hydrogen in air. Here, for the purpose of showing another potential application of
Rh NPs produced by LAL in water, Fazio et al. report some early results on their SERS activity by
considering the reference analyte Rhodamine 6G (R6G). By comparing the SERS spectrum of R6G on
Rh NPs with the Raman spectrum acquired on bare glass under the same conditions (Figure 18a,b),
the resulting enhancement factor is about 20, which shows the feasibility of using Rh NPs prepared
by this technique as SERS substrates. The time-dependence of the SERS signal of R6G discloses the
photo-induced degradation of the analyte adsorbed on the Rh/Rh-oxide NPs under the 457 nm laser
irradiation (Figure 18c,d). Remarkably, a prompt and well-resolved SERS response is observed after just
3 s of irradiation. Then, after 110 s of irradiation, the strongest characteristic peak of R6G (1650 cm−1 )
almost completely disappears (the same peak weakens by a factor of 0.4 after 22 s of irradiation).
The photo-activity of nanostructured Rh surfaces was reported previously [206]; the data in Figure 18
parallel such behavior, which requires a careful control of irradiation conditions to use Rh-based NPs
as a SERS platform. LAL-synthesized Rh/Rh-oxide NPs arrays suitably arranged as thin films show a
moderate SERS enhancement factor. Further optimizing the deposition conditions of the NPs is likely
to improve the SERS performance of such substrates in the UV spectral region, which is of relevance
for biological applications.
The photo-activity of nanostructured Rh surfaces was reported previously [206]; the data in Figure
18 parallel such behavior, which requires a careful control of irradiation conditions to use Rh-based
NPs as a SERS platform. LAL-synthesized Rh/Rh-oxide NPs arrays suitably arranged as thin films
show a moderate SERS enhancement factor. Further optimizing the deposition conditions of the NPs
Nanomaterials
is likely to 2020, 10, 2317
improve 29 is
the SERS performance of such substrates in the UV spectral region, which of of
50
relevance for biological applications.
18.(a)
Figure 18. (a)Raman
Raman spectrum
spectrumof R6G (10−4 (10
of R6G M solution.) drop cast
−4 M solution.) on glass
drop cast and (b–d) Time-dependence
on glass and (b–d) Time-
of the SERS spectra of R6G −4
(10 ofM solution) −4 M water
dependence of the SERS spectra R6G (10 MAsolution)
−4 drop of A10drop solution
of 10−4 M of R6G was
water solution castwas
of R6G on
the
castglass and
on the dried
glass andindried
air before
in airmeasurements; the Raman
before measurements; spectra spectra
the Raman were acquired using anusing
were acquired HR800an
micro-Raman
HR800 micro-Ramanspectrometer (Horiba,(Horiba,
spectrometer Jobin-Yvon, Longjumeau,
Jobin-Yvon, France), using
Longjumeau, theusing
France), 457.9 nm
the line
457.9ofnm
an
Ar + ion laser,+ setting the laser power at 1 mW. The integration times were varied from a few seconds
line of an Ar ion laser, setting the laser power at 1 mW. The integration times were varied from a few
up to 110up
seconds s to
tomaximize thetosignal
110 seconds to noise
maximize theratio.
signal to noise ratio.
3.4. Semiconductor Nanoparticles for the Degradation of Organic Pollutants

3.4. Semiconductor Nanoparticles for the Degradation of Organic Pollutants
Environmental pollution and the energy crisis, with the rapid expansion of industry, human
Environmental pollution and the energy crisis, with the rapid expansion of industry, human
settlements and the improvement of life quality, has been, in recent years, an emergency across
settlements and the improvement of life quality, has been, in recent years, an emergency across the
the entire globe. Globally, about the 80% of wastewater is discharged untreated from human
entire globe. Globally, about the 80% of wastewater is discharged untreated from human
agglomerations; huge amounts (millions of tons) of wastewater containing different toxic volatile
agglomerations; huge amounts (millions of tons) of wastewater containing different toxic volatile
(VOC) organic and inorganic pollutants (e.g., heavy metals) and toxic sludge, are released into the
(VOC) organic and inorganic pollutants (e.g., heavy metals) and toxic sludge, are released into the
environment without purification treatments. Among VOC, benzene, toluene and xylenes (BTX) are
environment without purification treatments. Among VOC, benzene, toluene and xylenes (BTX) are
the most common and dangerous contaminants in petroleum refining operations and liquid-liquid
the most common and dangerous contaminants in petroleum refining operations and liquid-liquid
extraction processes. The copresence of these compounds in the atmosphere with NOx under solar
extraction processes. The copresence of these compounds in the atmosphere with NOx under solar
radiation generates photochemical oxidants leading to higher concentrations of ozone. Therefore, if in
radiation generates photochemical oxidants leading to higher concentrations of ozone. Therefore, if
the past, attention was focused on water and fossil fuel resources availability, currently water-quality
in the past, attention was focused on water and fossil fuel resources availability, currently water-
problems and modern green technology for energy production are mandatory. In the recent literature
quality problems and modern green technology for energy production are mandatory. In the recent
we find a consistent interest on group II–VI semiconductor-based NPs used to produce clean and
literature we find a consistent interest on group II–VI semiconductor-based NPs used to produce
sustainable energy sources (solar cells and hydrogen generation) and to remove organic pollutants
clean and sustainable energy sources (solar cells and hydrogen generation) and to remove organic
(e.g., BTX) by photocatalysis.
pollutants (e.g., BTX) by photocatalysis.
Different conventional physical, chemical and biological routes, including oxidation, precipitation,
solvent extraction (e.g., sulfolane for BTX), distillation, bio-remediation, filtration, extraction,
photocatalysis, etc. for the degradation and remediation of both organic and inorganic pollutants
are adopted. However, these traditional methods are characterized by a rather low efficiency
and often high costs as well as they fail to sufficiently remove the emerging contaminants to the
levels required by discharge standard or required for wastewater reuse [217–219]. In light of this,
to improve the remediation performance, attention is being focused toward new approaches and
advanced technologies such as advanced oxidation methods (AOMs) involving nanomaterials.

Between them, nanophotocatalysis is one of most interesting AOM approaches. It is an environmentally
friendly method, with high working efficiency in removing pollutants also under mild conditions,
in reduction of byproducts, in the possibility to operate at ambient temperature and pressure with
contained costs if compared with traditional degradation processes.
Since this approach is new, problems in terms of regeneration and recovery of the catalyst caused
by adsorbed contaminants from nanomaterials must be evaluated. Recently, NPs or nanomaterials
used for organic contaminant degradation in wastewater treatment are often implemented in filtration
membranes and high surface area adsorbents also improving the reuse ability. However, despite many
research efforts, the practical application of nanoadsorption and nanophotocatalysis for the removal of
emerging contaminants remains limited.
Few researchers attempted wastewater treatment using nanocomposites made of carbon-based
materials or metal/metal oxide NPs such as TiO2 [220], ZnO [221], Pd [222], Fe3 O4 [223], cerium oxide
and semiconductors–noble metals [224]. With the characteristics of nontoxicity, good stability and a
special ability to oxidize, decompose toxic organic pollutants, resist corrosion, low cost and durability,
TiO2 and ZnO-based NPs are the most versatile semiconductor photocatalysts [225,226]. However,
they present a wide band gap (3.2–3.0 eV) that restricts their use under UV irradiation. To overcome
this drawback, the self-doping of TiO2 with Ti3+ atomic defects and the coupling with noble metal
NPs are the approaches proposed in order to enhance the TiO2 photoefficiency under visible/solar
light irradiation.
ZnO has been proposed as an alternative photocatalyst to TiO2 as it has the same band gap energy,
but exhibits higher absorption efficiency across a large fraction of the solar spectrum as compared to
TiO2 [227]. In order to evaluate the photosensitization of ZnO and TiO2 , Fenoll et al. [228] analyzed the
photo-degradation of fungicides in leaching water using the ZnO and TiO2 under solar irradiation: the
introduction of atomic defects such as those present in a nonstoichiometric metal oxide makes ZnO a
better photocatalyst than TiO2 under solar irradiation.
According to theoretical results [229,230], the extension into visible range should be also obtained
by introducing anionic dopants such as nitrogen [231], sulfur, fluorine species which confer a greater
stability to the catalyst with respect to the conventional transition-metal dopants, besides determining
a significant red shift of the band-gap into the visible range.
First reports on the photocatalytic effect of ZnO and TiO2 on organic and inorganic dyes under
irradiation date back to the first half of the 1900s by studies conducted by Eibner [232] and Keidel [233].
The effect of TiO2 and ZnO on the color fading under light irradiation was deeply discussed in the years
highlighting the superior photocatalytic activity sometimes of ZnO and other times of the TiO2 [234,235].
In particular, in 1931, Rao et al. observed the decomposition under solar irradiation of ammonia
salts-based fertilizers due to the presence in the soil of TiO2 and ZnO [236–238], while the mechanism of
photogenerated electron/hole (e− /h+ ) generation and recombination at different irradiation frequency
was first discussed by Frenkel [239] and later by Goodeve [240,241].
In the second part of ‘900, after Fujishima and Honda (1972) discussed the photocatalytic water
splitting on a TiO2 electrode [242], environmental applications (energy production and degradation of
organic pollutants) using solar light and semiconductor oxides became one of the attractive topics
of photocatalysis. The discovery of photoinduced water splitting together with other results such
as photoinduced redox reactions of adsorbed substances on TiO2 by UV irradiation [243] and the
decomposition of CN− ions in UV-irradiated aqueous TiO2 suspensions [244] have significantly
expanded the field of application of TiO2 based photocatalysts.
Since the 1980s, the overall, extensive effort has been conducted in the area of water treatment
using TiO2 , CeO2 , ZnO, CdS, WO3 , Fe2 O3 NPs [242,245], carbon-based nanomaterials, zeolites and
dendritic polymers [246] to detect and remove chemical and biological pollutants more efficiently,
exploiting the high surface area and the peculiar electronic and optical properties of materials with
Since the 1980s, the overall, extensive effort has been conducted in the area of water treatment
using TiO2, CeO2, ZnO, CdS, WO3, Fe2O3 NPs [242,245], carbon-based nanomaterials, zeolites and
dendritic polymers [246] to detect and remove chemical and biological pollutants more efficiently,
exploiting the high surface area and the peculiar electronic and optical properties of materials with
reduced dimensionality. Ultimately, ZnO and TiO2 are still today the most studied photocatalysts
Nanomaterials 2020, 10, 2317
for
31 of 50
environmental applications owing to their chemical stability, nature friendly, availability and low
cost.
reducedIt is dimensionality.
therefore useful,Ultimately, ZnO the
first to describe anddegradation
TiO2 are stillmechanisms
today the most thatstudied
involvephotocatalysts
them in presence for
environmental applications owing to their chemical stability, nature friendly,
of light irradiation and then to focus the directions of research related to water purification. One availability and low cost.
specificIt isobjective
thereforeofuseful, first toreview
the current describe theevaluate
is to degradation mechanisms of
the employment that involve them indoping
metal/nonmetal presenceTiOof2
light ZnO
and irradiation
NPs as and thenphotocatalysts
solar to focus the directions
in water of treatment.
research related
Then,toawater
case purification.
of real (low One specific
pollutants’
objective of the current
concentrations) industrial review is to evaluate
wastewater the employment
is analyzed, unlike what of metal/nonmetal doping
is generally reported in TiO and ZnO
the 2literature.
NPs The as solar photocatalysts
degradation mechanism in water treatment.inThen,
of pollutants watera case
on the of ZnO
real (low pollutants’
and TiO 2 surfaceconcentrations)
is similar and
industrial wastewater is analyzed, unlike what is generally reported in
is achieved by hydroxylation reactions mediated by oxygen radicals. In detail, electron (e−)/hole (h+) the literature.
pairsThe degradation
are generated bymechanism
semiconductor of pollutants
oxides underin water on the ZnO
irradiation withand TiO2 energy;
specific surface then,
is similar and is
reduction
achieved by hydroxylation − )/hole (h+ )
and oxidation reactions takereactions
place onmediated by oxygen
the photocatalyst radicals.
surface. In detail,involving
Reduction electron (e adsorbed O2,
pairs are generated by semiconductor oxides under irradiation
pollutants (P) and photo-generated electrons in the conduction band gives rise to oxidized freewith specific energy; then, reduction
and oxidation
radicals (O− ∙ reactions
2 , HO
∙
2 ), which, takein place
turn, on the photocatalyst
degrade surface.inReduction
organic pollutants the water.involving
Photoholes adsorbed O2 ,
(h+) in the
pollutants (P) and − ∙
valence band are photo-generated
highly oxidizingelectrons towardsinHthe 2O conduction
and O2 and band gives rise
produce to oxidized
reactive free such
species, radicals
as
(O∙ − · , HO
∙ ·
) , which, in turn, degrade organic pollutants in the water. Photoholes (h + ) in the valence
O and
2 OH,2 able to degrade most of organic molecules until their complete mineralization in H2O and
−· · ·
band
CO 2. are highly oxidizing towards H2 O and O2 and produce reactive species, such as O and OH,
able Formation
to degrade of most of organic molecules
intermediate species and until their complete
degradation mineralization
products in H2 O andhave
in the photocatalysis CO2 . been
deeply Formation
investigated of intermediate
in the earlierspecies
literature and[247–249].
degradation The products
main redox in the photocatalysis
reactions have been
are summarized by
deeply investigated
Horikoshi and Malato in[250,251]
the earlier asliterature
follows: [247–249]. The main redox reactions are summarized by
Horikoshi and Malato [250,251] as follows: −
𝑒 + 𝑂2 → 𝑂2−∙
e− +
𝑂2−∙ (𝑎𝑑𝑠) +O𝐻2+ → O−·∙
2 2 (𝑎𝑑𝑠)
→ 𝐻𝑂
+
O+2 (ads) + H∙ → HO·2 (ads+)
−·
ℎ + 𝐻 𝑂 → 𝑂𝐻(𝑎𝑑𝑠) + 𝐻 (14)
h+ + H22O → · OH (ads) + H + (14)
h+ +
ℎ +𝑂 −· (ads) → 2O∙· (ads)
O2−∙
2 (𝑎𝑑𝑠) → 2𝑂 (𝑎𝑑𝑠)
+
h + + P → P·∙++
ℎ +𝑃 →𝑃
Then, oxygen
Then, oxygen and
andpollutant
pollutantradicals
radicalsfurther
furtherreact
reactto to give
give oxidation
oxidation of of organic
organic products.
products. A
A schematic
schematic of of such
such reactions
reactions is reported
is reported in in Figure
Figure 19.19.
Figure
Figure 19.
19. Scheme
Scheme of
of redox
redox reaction.
reaction. CB:
CB: conduction
conduction band,
band, VB:
VB: valence
valence band.
band.
ZnO
ZnO and
and TiO22 unfortunately
unfortunately have have the
the same
same drawback
drawback related
related toto the
the fast
fast electron/hole
electron/hole
recombination
recombination that
thataffects
affectsthe
thephotocatalytic
photocatalytic activity. In addition,
activity. their their
In addition, wide wide
energy band gap
energy band in gap
the
UV range
in the (3.2–3.4
UV range eV) compared
(3.2–3.4 eV) comparedto the visible
to the light
visible energy
light (1.65–2.75
energy (1.65–2.75eV),
eV),strongly
stronglylimit
limitaa more
more
economical application
applicationininthethe pollutant
pollutant abatement
abatement [252,253]
[252,253] basedbased
on theonsolar
theirradiation
solar irradiation (the
(the fraction
fraction
of photonof energy
photonin energy
the UV <5%
inisthe UVinissolar
<5% in solar spectrum).
spectrum).
In an accurate and systematic study [254], the possibility of using solar-irradiated TiO2 for
the detoxification of methyl orange (MO) as a model pollutant compound was explored. Different
conditions, such as MO concentration, pH, TiO2 concentration and solar intensity were considered to
maximize MO degradation rate. By assuming a pseudo-first order kinetics and following the relation:
C
ln = −kapp t (15)
C0
where C is the concentration at time t and C0 is the concentration at time t = 0 of MO, the authors
determined the apparent first order rate constants in different times with different solar intensities
(Table 1). Although several studies reported the best experimental conditions to maximize the pollutant
oxidation rate by using semiconductor oxides, a nanocatalyst modification was however necessary to
further improve the catalytic performance under solar irradiation. As already mentioned, some of the
most investigated and performing strategies to modify absorption properties of ZnO and TiO2 are the
introduction of atomic defects and the design of new nanocomposite materials resulting by the coupling
of different semiconductor oxides, metals and carbon-based materials [255–260]. The improved
photocatalytic performance in the entire frequency range of the solar spectrum attained by the
so-called blue Titania, namely defective TiO2 (bearing oxygen vacancies and under-cordinated Ti+4 )
was demonstrated [261,262] not only towards pollutants but also in the water splitting processes [257].
The enhanced performance was attributed to the charge injection/recombination dynamics [263,264].
Table 1. Results on detoxification of methyl orange (MO) as under different conditions (MO
concentration, pH, TiO2 concentration and solar intensity). Reprinted from Ref. [254], Copyright (2002),
with permission from Elsevier.
Rate Constant k of Degradation of TiO2 (h−1 ) in Effect of Concentration on the Degradation Rate (h−1 ) during
Different Time with Different Solar Intensities W h/m2 April 2001
1st Rate Solar [MO] pH pH
Month k (465 nm) R2
Constant Intensity April 2001 before Reaction after Reaction
July 1999 0.6195 4480 2 × 10−3 M 0.0412 0.94 6.4 6.1
November 1999 0.367 2535 4 × 10−4 M 0.1329 0.96 6.4 6.0
December 1999 (cloudy) 0.2455 2177 8 × 10−5 M 0.2010 0.98 6.5 6.1
January 2000 0.3314 3060 4 × 10−5 M 0.6393 0.92 6.5 6.4
February 2000 0.6489 3419 1 × 10−5 M 0.2912 0.90 5.9 6.2
March 2000 0.7953 4255
May 2000 0.5445 4814
June 2000 0.4645 3969
October 2000 0.3491 3970
Doping with atomic defects can be achieved by different routes, ranging from vacuum
treatments, reducing thermal treatments [265,266] to hydrogen plasmas [267,268], yet one of the
more convenient, flexible and environmentally friendly strategies is to use LAL of semiconductor
oxide NPs dispersed in liquid (typically water). This leads to structural transformations in terms of
stable under-coordinated atoms, different oxidation state of transition metal in the oxide and oxygen
vacancies which play a fundamental role in the mechanism of photodegradation.
Chen et al. [269] demonstrated that the formation of Ti3+ species and a surface structural disorder
can be induced in titania NPs by LAL: the resulting modified catalysts exhibit good photocatalytic
performance under visible light towards the abatement of dyes. Moreover, Filice et al. [257] confirmed
a long living and an extended catalytic efficiency in the visible spectrum for water photo-splitting by
titania colloids, modified by nanosecond pulsed laser irradiation.
Another simple approach to improve the solar activity of TiO2 is the synthesis of TiO2 -based
composites with other transition metal oxides. In this context, photocatalytic oxidation of ethanol,
as a model for VOCs, was investigated by Fiorenza et al. [270] by introducing Co oxides into TiO2 :
TiO2 -CoOx composites exhibit a maximum decrease of the TiO2 band gap of about 0.2 eV when 1% (w.)
of CoOx is added to TiO2 (extrapolated band gap 3.03 eV). Moreover, in the same catalyst, a further
band gap at 2.3 eV was observed confirming the extended absorption in the visible range.
Recently, D’Urso et al. [259] prepared ZnO and ZnO/Au in the form of nanocolloids and nanorods
by picosecond pulsed laser ablation in water. Experimental results indicated gold decorated ZnO
nanorods as high photodegradation efficiency catalysts towards methylene blue (MB) dye, under UV
light irradiation, as compared to bare ZnO. In this regard, doping with metals could promote
photocatalysis by different concomitant events:
• A decrease in the band gap energy due to the increased structural disorder;
• A strong absorption in the visible range, due to the Surface Resonance Plasmon (SPR) of free
electrons (the same effect was observed in Ag-TiO2 catalysts) [260,271,272], favors the injection
of photo-excited SPR electrons into the conduction band (CB) of TiO2 , thus creating separated
electrons-hole pairs and hindering the recombination process [273].
• Metals can act as reservoir, promoting interfacial electron transfer processes from the semiconductor
CB toward metal NPs, being the Fermi level of the metal lower than the CB of the semiconductor,
leaving holes in the valence band (VB) of the photocatalyst.
• Electrons transferred from Au NPs surface to the oxide can be caught by oxygen atoms giving
active O2 − species with the increase of the photo-catalytic activity [274].
In the literature, several studies reported that titania-based photocatalyst modified with Pt, Cu, Pd,
Rh, Ni [260,275–280] show almost the same features in terms of efficient charge transfer phenomena,
thus exhibiting a higher efficiency both in the UV and in the visible range. Ultimately, photo-activated
reactions as 2-propanol degradation, chemo-selective oxidation of alcohols, efficient phenol removal
from aqueous solutions by Ag in photoactivated ZnO-Ag [281] are other reported examples of enhanced
efficiency in modified catalysts.
We remark that most of the studies on photo-degradation are related to dye molecules, alcohols or
other molecules in the field of pharmaceuticals (ibuprofen, ciprofloxacin, etc). However, different kinds
of pollutants are contained in industrial waters and wastewaters, from agricultural pollutants, inorganic
pollutants (metals compounds, inorganic salts, heavy metals, mineral acids), plastic pollution, VOC.
An internet search with keywords “photodegradation of volatile organic compounds” resulted in about
700 hits, compared with the 7000 for “photodegradation of MB” and 400,000 by editing the keyword
“photodegradation”. Literature lacks systematic investigation/rationalization of these dangerous
contaminants. Among VOC, benzene, toluene and xylenes (BTX) are the most common and unsafe
compounds in petroleum refining operations and liquid-liquid extraction processes. The copresence of
these in the atmosphere with NOx and solar radiation generates photochemical oxidants leading to
higher levels of ozone. The abatement of these contaminants is therefore mandatory.
Here we investigate the removal of BTX from contaminated industrial waters through
photocatalysis by using modified TiO2 nanocatalysts with the introduction of atomic defects or
by joining TiO2 with 3 wt%. AuNP. In the first case, commercial anatase TiO2 (Aldrich) was treated
by laser irradiation in liquid, using the third harmonic (355 nm) of a Nd:YAG pulsed laser (10 ns,
10 Hz). The treatment was carried out at pH 9 for 60 min. The second modified catalysts (AuTiO2 )
was obtained, first by synthesizing Au NPs by laser ablation in water, by focusing the first harmonic
(1064 nm) of a Nd:YAG on a pure gold (99%) target. Then a dispersion at 3% (w.) of Au NPs and
TiO2 in water was prepared. All catalysts were characterized by Raman, Diffuse Reflectance and
Photoluminescence spectroscopies.
BTX aqueous solutions used for BTX photodegradation, came from an aromatic hydrocarbon
extraction process that uses sulfolane as extraction solvent, in particular from a tank that collects
waters from various sections of the BTX production plants, including the sulfolane extraction sections.
In the Table 2 the percentage composition of employed industrial waters are reported together with the
pH value. Industrial waters were then diluted until a concentration in benzene of 10−3 M, being the
component present at higher concentration. The photodegradation of the diluted industrial waters
was conducted with a solar simulator and was monitored recording the UV–Vis optical density in
the 225–275 nm range [282]. Photocatalytic data showed that the modifications induced by the laser
treatment of TiO2 led to a bandgap decrease as compared to the bare TiO2 due to the introduction of
oxygen vacancies and defects inside theTiO2 , as shown in Figure 20. The bandgap value, calculated
by a Kubelka–Munka function (i.e., F(R) plotting (F(R)hν)1/r as a function of the photon energy (hν)),
exhibits a strong decrease after laser irradiation, from the 3.17 eV in unmodified TiO2 to 3.03 eV in the
laser-treated sample. It is worth to notice the inset of the same figure, where a zoom of the lower energy
(2.70–1.80 eV) region is reported. In this region, the contribution of Au NPs to the optical absorption
is recognizable. Au absorption feature is centered in the middle of the visible range with an energy
induced by the laser treatment of TiO2 led to a bandgap decrease as compared to the bare TiO2 due
to the introduction of oxygen vacancies and defects inside theTiO2, as shown in Figure 20. The
bandgap value, calculated by a Kubelka–Munka function (i.e., F(R) plotting (F(R)hν)1/r as a function
of the photon energy (hν)), exhibits a strong decrease after laser irradiation, from the 3.17 eV in
Nanomaterials
unmodified2020,TiO10, 2317
2 to 3.03 eV in the laser-treated sample. It is worth to notice the inset of the same
34 of 50
figure, where a zoom of the lower energy (2.70–1.80 eV) region is reported. In this region, the
contribution
around 1.93 eV,of Au NPs to the
meanwhile optical
there is notabsorption is recognizable.
any adsorption Au range
in the visible absorption
for thefeature is centered
other two in
catalysts.
the middle of the visible range with an energy around 1.93 eV, meanwhile there is not any
This structure modification results in enhanced photoactivity of the laser-treated TiO2 sample towards adsorption
in the
the visible range
degradation for the
of organic other two
pollutants catalysts. waters
in industrial This structure
compared modification
to un-modifiedresults
TiO2in. enhanced
photoactivity of the laser-treated TiO2 sample towards the degradation of organic pollutants in
industrial waters Table
compared to un-modified
2. Percentage compositionTiOand
2. pH of employed industrial waters.
pH and pH of9.1
Table 2. Percentage composition employed industrial waters.
Benzene 90.3%
pH 9.1
Toluene
Benzene 6.1%
90.3%
Toluene
m-xylene 6.1%
0.85%
m-xylene 0.85%
o-xylene 0.46%
o-xylene 0.46%
p-xylene
p-xylene 0.32%
0.32%
Etylenbenzene
Etylenbenzene 1.32%
1.32%
Aromatics
Aromatics 1060
1060 mg/L
mg/L
Figure 20. Energy bandgap calculation by Kubelka-Munka transformation for the three catalyst. Inset:
Figure 20. Energy bandgap calculation by Kubelka-Munka transformation for the three catalyst. Inset:
a zoom of the lower energy region was set up the Au NPs adsorption (right side). In the inset is reported
a zoom of the lower energy region was set up the Au NPs adsorption (right side). In the inset is
the micro-Raman spectra of as prepared TiO2 (red line) and of blue Titania (blue line) with a zoom of
reported the micro-Raman spectra of as prepared TiO2 (red line) and of blue Titania (blue line) with
the TiO2 Eg anatase peaks before and after the laser treatment.
a zoom of the TiO2 Eg anatase peaks before and after the laser treatment.
To better understand the effect of laser irradiation on TiO2 , blue titania NPs were characterized by
Raman spectroscopy. In the inset of Figure 20 is reported a zoom of the Eg peak of the Raman spectra of
as prepared TiO2 and of the irradiated one. Micro-Raman spectra, obtained using the 530 nm excitation
wavelength, of commercial TiO2 agree with the typical peak position of the anatase phase (red curve).
Its characteristic peak: Eg (144 cm−1 ) is very intense. However, after laser irradiation, a significant
change of the peak intensity and a shift of anatase vibrational features is observed. Such a change
is ascribed to the generation of oxygen vacancies in the atomic structure of the catalyst. The trend
observed is analogous to that reported [283], in samples for which the calculated value of the O/Ti
atomic ratio is reduced to 1.88 with respect to the native value of 2. We outline that the presence of
oxygen vacancy defects, as already discussed, decreases the band gap value and also generates more
active Ti3+ sites.
The UV–Vis spectrum in the 275–230 nm range of BTX aqueous solution is reported in Figure 21a
together with that of pure benzene, toluene and xylene, according to the aromatic concentration
reported in the table in Figure 21. By fixing the catalyst concentration in all experiments to 0.15 mg/mL,
we have observed a negligible contribution of the catalyst into the BTX absorption spectra. The kinetics
of disappearance of aromatic mixtures is displayed in Figure 21b (an adsorption period in the dark of
30 min). Photocatalytic degradation was performed in a closed box kept at low temperature in an ice
bath to avoid evaporation of BTX from the solution, under strong stirring condition. The intensity
decrease of the band at 254 nm, mainly associated to benzene electronic transitions [282], was monitored
as a function of the irradiation time in a range of 80 min. In the presence of blue titania NPs, 76% of
benzene, the most abundant component in the employed industrial waters, is removed after 80 min;
after the same irradiation time, when AuTiO2 NPs were employed as photo-catalyst a residual less than
1% of benzene in water was detected. Moreover, we obtained that, after only 5 min, the percentage of
BTX decreased by 53% when Au-decorated TiO2 is used; instead, when blue and commercial TiO2 are
employed
Nanomaterialsas a photocatalyst,
2020, 10, x BTX decreases by 26% and 14%, respectively, during the same time. 35 of 50
Figure 21. UV–vis spectra of BTX/sulfolane aqueous solution in presence of TiO2 laser-treated catalyst
Figure 21. UV–vis spectra of BTX/sulfolane aqueous solution in presence of TiO2 laser-treated catalyst
under solar lamp irradiation (a); calculated kinetic constant of the photodegradation for the three
under solar lamp irradiation (a); calculated kinetic constant of the photodegradation for the three
catalyst (b); kinetic constant for the photodegradation reaction of benzene, toluene and xylene in pure
catalyst (b); kinetic constant for the photodegradation reaction of benzene, toluene and xylene in pure
water (10−3 M) compared with the BTX mixture in presence of blue Titania catalyst, under solar light
water (10−3 M) compared with the BTX mixture in presence of blue Titania catalyst, under solar light
irradiation (c).
irradiation (c).
By a comparison of kinetic constants of photodegradation, evaluated by considering the peak
By adecrease
intensity comparison of kinetic
at 254 nm andconstants
by usingofa photodegradation,
pseudo-first order evaluated by considering
reaction kinetic model, we thefound
peak
intensity
an increasedecrease
of Kappatstarting
254 nmfrom
and by using
bare TiOa2 pseudo-first
with a valueorder
of 1.4reaction
× 10−2kinetic
min−1 model, we found
up to blue an
TiO2 of
increase−2of K −1
app starting from bare TiO 2 with a value of 1.4
−2 × 10 −2
−1 min −1 up to blue TiO2 of 3.8 × 10−2
3.8 × 10 min and TiO2 loaded with Au NPs of 8.3 × 10 min . It is clear that the interaction of
min−1 and TiO2 loaded with Au NPs of 8.3 × 10−2min−1. It is clear that the interaction of Au with the
surface of the TiO2 catalyst enhances the catalytic process, thus degrading more quickly almost the
entire pollutant. The improvement in the efficiency of the photodegradation process is not only
related to the lower value of the energy bandgap of the catalyst (blue titania presents the lowest
energy BG with respect to the other two catalysts), but it seems that the main responsible of the great
Au with the surface of the TiO2 catalyst enhances the catalytic process, thus degrading more quickly
almost the entire pollutant. The improvement in the efficiency of the photodegradation process is not
only related to the lower value of the energy bandgap of the catalyst (blue titania presents the lowest
energy BG with respect to the other two catalysts), but it seems that the main responsible of the great
improvement of the photoefficiency is due to the presence of Au NPs [260,271,272], that, thanks to
the SPR and high electron density, are able to enhance the electron transfer from the Au NPs to the
catalyst [273,274].
To better understand the defect doping effect, blue titania was used as a catalyst to degrade single
components of the BTX mixture. For this purpose, three solutions containing commercial Benzene,
Toluene and Xylene, respectively, were prepared in millipore water at the same concentration of 10−3 M.
The photodegradation experiment was conducted under the same experimental conditions above
described. The photoefficiency of blue titania towards the degradation of single aromatic compounds
(benzene, toluene and xylene) 10−3 M in millipore water are compared in Figure 21c. After 20 min,
all pollutants reduced by 95% with respect to the initial concentration. It is to be noted that the lowest
kinetic constant is obtained for the degradation of benzene. However, this value results three times
higher than that obtained for BTX in industrial waters. It seems [284] that benzene degrades less
quickly when it is mixed with toluene. This finding could explain the difference in the kinetic rate and
the lower value of kinetic constant related to the degradation of the BTX mixture, in which benzene is
the most abundant component and toluene the second one.
4. Conclusions
In this review, we reported on various laser-based methods for the generation of colloids with a
tight control on their properties (the purity of the product, the selectivity in the crystal structure of
the oxide, a fine control of the particle size distribution). The peculiar chemical–physical properties that
new nanomaterials produced by LAL can offer have been described in view of specific technological
applications and showed to be competitive with those of conventional chemical procedures. However,
LAL colloids are not yet applicable on a large scale. To reach this purpose, we considered it essential
to analyze in depth the fundamental LAL mechanisms, taking into account the multiple time-scale
transient processes that take place under the different experimental conditions which, ultimately,
determine the nanocolloids properties.
5. Outlooks
Since about 2010 there has been a growing research and development of third-generation
nanotechnologies, which are characterized by their multiscale architecture (i.e., involving macro-,
meso-, micro- and nanoscales together) and three-dimensionality. Some applications driving the
developments of third generation nanotechnologies are biosensors or drug-delivery vectors modelled
on biological templates. After 2015, the fourth-generation nanotechnologies employ “molecular
manufacturing”, to achieve multifunctionality and the control of functions at a molecular level.
The global deterioration of water, soil, and the atmosphere by the release of toxic chemicals from the
ongoing anthropogenic activities is becoming a serious problem throughout the world. Thanks to the
remarkable advances in nanotechnology and the urgent need to develop green, robust and economic
approaches for innovative biomedical purposes and environmental remediation, LAL-prepared
nanomaterials could be successfully used in biomedicine, in wastewater treatment systems, for the
production of clean and sustainable energy sources (e.g., solar cells and hydrogen generation systems)
and for the removal of organic pollutants by photocatalysis.
Despite their great potential, some aspects of the LAL processes and of their products need
to be optimized. Strong efforts should be devoted to achieve higher colloidal stability, preventing
aggregation phenomena and the formation of larger particles, which, for instance, affect the catalytic
properties and could even lead to the inactivation of the material. Efforts should also be devoted
to the embedding of plasmonic NPs in bulk-heterojunction solar cells to promote photo-conversion.
Furthermore, to achieve the gram-scale production that is required for industrial applications it is
essential to properly define a LAL procedure and protocol.
Although LAL-synthesized NPs are referred to as ligand/surfactant-free, they are not totally naked
and still bear their own surface chemistry, i.e., some of the NP surface atoms are oxidized or complexed.
Presently, an appropriate protocol to realize performance-oriented colloidal synthesis and processing
in order to prepare more isochronous surface modification in metal and semiconductor NPs (also
within a polymeric matrix) is still not defined. The latter is an urgent request of modern manufacturing
based on laser ablation to make possible in-situ engineering, thereby opening the way to fabricate
functionalized (or coated) NPs.
Moreover, nanostructures have dimensions which are similar to those of subcell structures,
like receptors, and for this reason they can strongly interact. This is an important opportunity which
can be exploited, as above reported, using nanostructures with engineered functionalizations, for a
theranostic targeted nanomedicine. Indeed, since NPs produced by LAL have appealing and controlled
plasmonic properties, spanning from the visible to the UV region, they are excellent platforms for SERS
applications, even though significant efforts should be spent to obtain a higher signal-to-noise ratio in
the UV spectral region. To this purpose, further studies closely combining the features of LAL with the
application demands of various functional materials are still necessary.
Author Contributions: All authors have contributed in equal manner to the manuscript writing. Conceptualization,
E.F. and M.S.; writing, all the authors; review and editing, E.F., L.D. and B.G. All authors have read and agreed to
the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: Financial support by the University of Padova is acknowledged by M.M. and L.L. (#04SID2016)
and by M.G. and F.B. (#08SID2017). We thank Stephan Barcikowski for fruitful discussions.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design of the
study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to
publish the results.
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nanomaterials

Keywords: colloids; laser synthesis; plasmonics; sensing; biomedicine; catalysis; pollutants

Nanomaterials 2020, 10, 2317; doi:10.3390/nano10112317 www.mdpi.com/journal/nanomaterials

2. LAL Synthesis Methods: Principle, Process Parameters and Liquids Effects on

Figure 2.2. Different

Consequently, Equation (3) becomes:

Figure 9. Illustration of the optical

Figure 10. Illustration

Figure 11. Illustration

2.3. LAL-Based Techniques for Nanomaterials Synthesis and Processing

εalloy (ω) = x εAu (ω) + (1 − x) εAg (ω) (12)

where x denotes the Au molar fraction in the Au−Ag alloy [149].

Figure 14. Absorption

3.3. Metal Oxide Nanostructures for UV-SERS Sensing Applications

To date, the Rh nanostructures investigated were grown by electrochemical roughening of Rh

relevance for biological applications.

3.4. Semiconductor Nanoparticles for the Degradation of Organic Pollutants

advanced technologies such as advanced oxidation methods (AOMs) involving nanomaterials.

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