Soft Matter

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Recent advances in the design and use of

Pickering emulsions for wastewater
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19, 818 treatment applications

Zygimantas Gricius and Gisle Øye*

Pickering emulsions have recently emerged as versatile systems capable of targeting many applications
of wastewater treatment. The unique properties, which include high emulsion stability, easy preparation,
low toxicity, and stimuli-responsiveness, pave the way for advances in common pollutant control
processes. This review aims to provide a comprehensive overview on different aspects in the Pickering
emulsion design focusing on the key structural relations and their implications in specific applications.
The first section is dedicated to the critical parameters governing the Pickering emulsion type, droplet
size and stability. Furthermore, a section describing methods for demulsification and particle recovery is
Received 1st November 2022, included, in which various stimuli have been explored. Finally, the most potent applications of Pickering
Accepted 3rd January 2023 emulsions such as photocatalytic degradation, adsorption, extraction, and separation of common
DOI: 10.1039/d2sm01437h wastewater pollutants are presented and discussed with a great deal of attention towards the efficacy,
current limitations, and future potential. Recognizing the rise of innovative Pickering emulsion solutions
[Link]/soft-matter-journal is expected to induce profound effects facilitating the technology transfer to industrial processes.

1. Introduction worldwide have no or little access to clean and sanitized water

supply, and millions of people die of severe waterborne dis-
Ever since the start of the industrialization era, the demand for eases annually.2 As a result, both chemical pollution and global
freshwater resources has been increasingly growing, which freshwater use were listed among the 9 critical problems
poses many challenges for the developing nations facing rapid referred to as planetary boundaries, defined by a group of
urbanization, population growth and chemical contamina- leading environmental scientists.3 Similarly, a report made by
tion problems.1 It is estimated that around 4 billion people the United Nations Environment Programme (UNEP) stated
that nearly all documented issues associated with the world-
wide toxic contamination and their implications for human
Ugelstad Laboratory, Department of Chemical Engineering, Norwegian University of
Science and Technology (NTNU), 7491, Trondheim, Norway.
health can be related to industrial and mining activities.4 One
E-mail: [Link]@[Link], [Link]@[Link] of the key underlying reasons behind these trends is the rapid

Zygimantas Gricius is currently a PhD candidate under the supervision of Prof. Gisle Øye at the
Norwegian University of Science and Technology (NTNU), where he uses Pickering emulsions to
photocatalytically degrade common organic wastewater pollutants. He obtained his Master in
Applied Chemistry from Technical University of Denmark (DTU) and later worked in medical device
industry as an engineer before joining Ugelstad Laboratory at NTNU. His research interests include
polymers, colloids, surface chemistry, thermodynamics, and catalysis.
Gisle Øye is professor and group leader at Ugelstad Laboratory, the group for colloid and polymer
chemistry, at Department of Chemical Engineering at the Norwegian University of Science and
Technology (NTNU). His research interests include experimental studies of physicochemical properties
of colloidal and emulsion systems of interest in industrial and wastewater applications.

Zygimantas Gricius

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expansion of industries that lack low-cost high efficiency water (adsorption, chemical coagulation, biodegradation) suffers
treatment technologies to treat the wastewater resulting in a from multiple drawbacks making a ‘‘one size fits all’’ solution
discharge of micropollutants and contaminants into the nat- difficult to achieve.12–14 The adsorption method is simple and
ural water cycle.5,6 versatile, but the pollutant is only transferred from one phase
Depending on the industry, a diverse group of organic to another, without achieving the degradation effect.15 What is
compounds can be found, including organic dyes, organic more, regeneration of the adsorbent is limited. The chemical
cyanides, heterocyclic compounds, and polycyclic aromatic coagulation method can remove suspended solids effectively
hydrocarbons that are characterized by high toxicity and but lacks versatility for different compositions of wastewater.16
high-enough concentrations to be considered an environ- Finally, the biological treatment, despite being the most effi-
mental hazard.7 A vast amount of water is also produced during cient, is susceptible to high concentrations of pollutants
that can affect the activity of microorganisms.7 A common
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oil and gas recovery, where the discharge water makes up the
largest volume waste stream.8–10 The composition of produced way to optimize the pollutant removal process involves the
water tends to vary both in terms of salinity and the nature of combination of all the approaches and is generally driven by the
organic compounds, but the most abundant organic com- biological treatment within the integrated activated sludge treat-
pounds in produced waters are water-soluble low molecular ment plant, where the sludge undergoes a series of mecha-
weight organic acids and monocyclic aromatic hydrocarbons.10 nical and physiochemical steps, such as oil–water separation and
The presence of these compounds results in numerous adverse coagulation.17 Despite the complexity of the process flow, the use
effects, including corrosion of production pipes and the overall of reclaimed water is limited owing to the stringent and constantly
toxicity of produced water.11 Although the low molecular weight variable pollutant level requirements.18 A summary of require-
organic acids are known to be readily biodegraded by bacteria, ments and applications for reclaimed water is given in Table 1. As
fungi, and plants, various naphthenic acids (NAs), such as seen from the table, the pollutant levels are adjusted with respect
alkylated benzoic acids or alicyclic carboxylic acids, are difficult to the risk for a direct human exposure to reclaimed water.
to remove by conventional methods.10 At present, each of the Ultimately, the regulatory pressure imposed on the compa-
industrially relevant organic wastewater treatment solutions nies responsible for reclaiming this water and finding ways to

Table 1 Requirements and applications for reclaimed water usage

Water reuse Treatment goalsab Examples of applications

Urban use: unrestricted r10 mg L BOD1
Landscape irrigation (parks, playgrounds, school yards),
r2 NTU fire protection, construction, ornamental fountains,
No detectable fecal coliform/100 mL recreational impoundments, in-building uses (toilets,
1 mg L 1 Cl2 residual (min) air conditioning)
Urban use: restricted r30 mg L 1 BOD Irrigation of areas where public access is infrequent
r30 mg L 1 TSS and controlled (golf courses, cemeteries, residential,
r200 fecal coliform/100 mL greenbelts)
1 mg L 1 Cl2 residual (min)
Agricultural irrigation: food crops r10 mg L 1 BOD r 2 NTU Crops grown for human consumption and consumed
No detectable fecal coliform/100 mL uncooked
1 mg L 1 Cl2 residual (min)
Agricultural irrigation: non-food crops r30 mg L 1 BOD Fodder, fiber, seed crops, pastures, commercial nurseries,
r30 mg L 1 TSS sod farms, commercial aquaculture
r200 fecal coli/100 mL
1 mg L 1 Cl2 residual (min)
Impoundments: unrestricted BOD5: r10 mg L 1 No limitations on body contact (lakes and ponds used for
r2 NTU swimming, snowmaking)
No detectable fecal coliform/100 mL
1 mg L 1 Cl2 residual (min)
Impoundments: restricted r30 mg L 1 BOD Fishing, boating, and other noncontact recreational
r30 mg L 1 TSS activities
r200 fecal coli/100 mL
1 mg L 1 Cl2 residual (min)
Environmental enhancement Equivalent to restricted impoundments Artificial wetlands, enhanced natural wetlands, and
sustained stream flows
Groundwater recharge Site-specific Groundwater replenishment, saltwater intrusion control,
and subsidence control
Industrial reuse Equivalent to restricted impoundments Cooling system makeup water, process waters, boiler feed
water, construction activities, and washdown waters
Potable reuse No detectable total coliform/100 mL Blending with municipal water supply (surface water
1 mg L 1 Cl2 residual (min) or groundwater)
r2 NTU
r2 mg L 1 TOC of wastewater origin
a b
Adapted from ref. 19. BOD5: biochemical oxygen demand; NTU: nephelometric turbidity units; TSS: total suspended solids; TOC: total organic
carbon.

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release it back into the local environment creates a demand for

research done on the development of low-cost and environmen-
tally friendly methods that could serve a wide range of degrad-
able pollutants.20 Numerous advances have already been made
on the laboratory scale treatment of organic acids by employing
methods like nanofiltration,21 membrane filtration,22 ozona-
tion,23 or chemical coagulation,24 but these processes are yet to
be optimized for upscaling. Therefore, the implementation of
novel degradation techniques of pollutants for wastewater
treatment remains an important milestone for remediation of Fig. 1 Comparison of (a) classical and (b) Pickering emulsions.
the large volumes of industrial effluents.25
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The use of functional nanomaterials targeting wastewater

treatment has recently emerged as one of the leading research pollution, increased stability, recycling ability and resistance
fields that could facilitate the transition from the laboratory towards pH or temperature changes.31,32 Moreover, there has
scale to various industrial plants worldwide.26,27 The unique been a tremendous breakthrough in the use of PEs for a variety
features like small particle size, high surface-to-volume ratio, of catalytic applications offering advantages such as large active
high surface energy and the catalytic properties give rise to catalyst areas due to less particle agglomeration when adsorbed
performance far superior to conventional wastewater treatment at liquid–liquid interfaces and the possibility to recover cata-
methods.20 This potential has already been demonstrated by lysts by demulsification.29,33 Many studies have demonstrated
implementing nanomaterials in photocatalysis, adsorption, flexibility of the system design by varying particle types, emul-
membrane filtration and chemical disinfection for an efficient sion parameters and the morphology of Pickering emulsifiers
pollutant degradation.28 Among the nanoparticle systems making it possible to carefully adapt PEs for a wide range of
applied for these applications, emulsions stabilized by solid applications.34–38
particles, so-called Pickering emulsions (PEs), have been
identified to be perfectly suitable for environmental applica- 2.1. Emulsion stability
tions.29,30 As result, numerous PE systems have been developed
The feasibility of a certain Pickering emulsion system for
claiming potential to replace the conventional wastewater
pollutant treatment cannot be assessed without ensuring sta-
treatment methods each of which posing individual require-
bility of the emulsion in a wastewater of interest. If successfully
ments on the particle type, morphology, and functionality. For
stabilized, the emulsions exhibit a long-term stability against
example, only the particles with a certain band gap can be used
coalescence or Ostwald ripening.39 Just like in the classical
for photocatalysis, while a porous nature leading to high sur-
emulsions, both the design of formulation and the process of
face area is an essential criterion for PEs used as adsorbents.
emulsification are of immense importance: the thermodyna-
However, the main advantages originate from the emul-
mically driven particle adsorption can be kinetically controlled
sion stability, tunability and recyclability, opening a pool of
by rheology and mass transfer of particles to interfaces.40
innovative particle engineering strategies. The applicability of
Various stabilization theories have been proposed throughout
Pickering emulsions is not limited to the direct use of as-
the years, but the commonly accepted mechanism of stabili-
prepared emulsions – on the contrary, the emulsification can
zation is thought to be achieved by creation of a steric barrier
be exploited to produce high performance functional materials
composed of solid particles adsorbing at the oil–water inter-
surpassing the limits of the PEs alone. Since the potential of
face.32,41 This mechanism was supported by many studies via
PEs in wastewater treatment applications has just recently been
theoretical discussions and thermodynamic calculations.42,43 Both
realized, no reviews regarding the topic have been published.
theoretical and experimental relations have been derived pointing
This review explores the roles, key parameters and the most
to the wettability and morphology of solid particles being the
potent applications associated with the use of Pickering
key parameters governing the stability of Pickering emulsions.44
emulsions in wastewater treatment.
Additional parameters were found to be the oil type, particle
concentration, size, phase volume fraction, pH and ionic
strength.31,32 The summary of these parameter relations will
2. Pickering emulsions: key be briefly presented in the following sections.
parameters and stability
Pickering emulsions are emulsions in which particles accumu- 2.2. Particle wettability
late at the interface between two immiscible liquids and act as It has been shown that although Pickering emulsions can be
stabilizers of the dispersed drops against coalescence (Fig. 1). stabilized in a kinetic sense, they are not thermodynamically
While most emulsion-based applications are dominated by the stable.46 However, high degrees of packing and negative values
use of conventional surfactants, Pickering emulsions have of the Gibbs free energy of particle adsorption at the oil–water
emerged as an alternative displaying very attractive proper- interface can be attained provided that particles exhibit partial
ties including low cost, low toxicity, reduced environment wetting, which can be determined by evaluating a tri-phase

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are feasible with submicron particles, therefore completely

new analytical pathways had to be explored.43,56 Two main
categories of methods can be defined, namely the ensemble
methods and single-particle methods, which are well explained
in the literature.57–59

2.3. Oil type and volume fraction

The previously defined Young’s equation illustrates the impor-
Fig. 2 Influence of a tri-phase contact angle on the Pickering emulsion tance of the oil phase in terms of the interfacial tension exerted
type. Reprinted from ref. 45 with permission from Elsevier. at the particle–oil and oil–water interfaces, gpo and gow, respec-
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tively. These parameters would directly influence the particle

adsorption energy thus the kinetic stability of the emulsions.
contact angle y at the three-phase region between the particle,
In applications, where the emulsion formation in wastewaters
water phase and the oil phase (Fig. 2): if the particle is hydro-
can be performed in-situ (photocatalysis, adsorption), each
philic (contact angle o901), the water phase will be favored as
hydrophobic component has a unique contribution to the
the continuous phase, thus an oil-in-water (O/W) emulsion
overall interfacial tension of droplets. Consequently, the pollu-
will be preferred.47,48 Conversely, the hydrophobic particles
tants shall preferably be analyzed prior to the particle design
(contact angle 4 901) will drive the formation of W/O emulsions.
activities so that an optimal emulsion stability window is
This phenomenon stems from the changes in the particle adsorp-
found.60,61 In general, numerous model oil phases have been
tion free energy (eqn (1), spherical particle case), which defines
explored including Pickering emulsions formed with silicone
the energy required for the solid particles to escape from the
oil,55 1-methylnaphthalene,62 hexadecane, heptane, or trichloro-
oil–water interface – the higher the energy, the stronger the
ethylene.63
adsorption to the interface. In general, Pickering emulsions show
Another aspect that relates to the stability and the degrada-
a much greater particle adsorption energy compared to classical
tion performance is the volume fraction of oil, which affects the
surfactant-based emulsions.40
droplet size and the type of emulsions.57,65,66 The variation of
DGads = pr 2gw–o(1 |cos y|)2 (1) droplet size was observed by increasing the ratio of the oil
phase in O/W PEs while keeping the graphene oxide particle
Looking back at the equation, the highest energy is reached concentration constant.65 With the increasing dispersed phase
when the cos(y) = 901 and it steadily decreases as the contact ratios, the excess surface area of the droplets cannot be
angle moves away from that value. This results in the inability stabilized to the same extent without proportionally increasing
to form stable Pickering emulsions at very low and very high the solid particle concentration, therefore larger droplets
contact angles as the particles remain dispersed in their pre- are being formed to compensate for the insufficient number
ferential phases.49 Another aspect of the equation is the quad- of stabilizing particles (Fig. 3), an effect called ‘‘limited coales-
ratic size dependency: since large particles have a larger area cence’’.67 This correlation has tremendous effects in most
contacting oil and water, they possess a larger adsorption wastewater treatment applications as the processes are gener-
energy. Although this relationship alone undermines the ally dependent on the effective surface area.
potential use of nanoparticles for Pickering emulsions, effects
like higher packing density and enhanced surface area puts 2.4. Effects of particle concentration, shape, and size
nanoparticles in the list of highly attractive Pickering emul- Having highlighted the main criteria for solid particle adsorp-
sifiers.50 The impact of particle wettability creates a demand for tion leading to emulsion stability, one should consider other
studies that are focused on surface modification of the solid physiochemical parameters such as particle concentration,
particles with an aim to attain an amphiphilic character.31,32 size, and shape, which are often used to optimize systems for
Several strategies exist in pursuit of the goal, but the most a specific application. Although there have been many reviews
common approaches are physical adsorption and chemical on these trends,32,40,57 certain parameters are more tunable
grafting.51–55 than the others. For example, the concentration of solid parti-
Having defined a tri-phase contact angle as an important cles has an inverse effect on the equilibrium emulsion droplet
descriptor affecting the kinetic emulsion stability, one should size as opposed to the volume fraction effect, thus in waste-
investigate the means of experimental characterization. A com- waters containing high amounts of oil phase, it might be
mon way to express a tri-phase contact angle is by using economically beneficial to vary the particle concentration
Young’s equation,2 which states that the contact angle is a instead of diluting the volume phase. In situations where
function of the particle–liquid interfacial tensions gpo and gpw.: emulsion stability is difficult to achieve, one can try to modify
cos(yw) = (gp–o gp–w)/gw–o (2) the particle shape such that the particle packing density would
surpass the particle adsorption stabilization energies typically
Unfortunately, neither the classical contact angle measuring seen for the spherical particles.68–70
method by optical observation of drops deposited onto a solid Finally, one of the key decisions in Pickering emulsion
surface nor the conventional interfacial tension measurements design is the size range of the stabilizing particles. Despite

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Fig. 3 Typical representation of the mechanism controlling the size of a solid-stabilized emulsion. Reprinted from ref. 64 with permission from Elsevier.

the interfacial adsorption energy scaling with the square of increasing as the particle size of silica nanoparticles became
particle radius, it is known that both higher packing density larger although the size difference between 5 and 12 nm was
and large catalytic surface areas can be achieved by decreasing small (Fig. 4).71
the particle size.72,73 However, it has been reported that having
the particles too small may also have adverse effects on the 2.5. pH and ionic strength
emulsion stability due to variation of the wettability with Pickering emulsion sensitivity towards pH and ionic strength
respect to the particle size.74 For their part, Binks & Lumdson opens new possibilities for tailoring the emulsion stability
showed that the stability of PEs against sedimentation increased windows owing to alterations in particle wettability and zeta
upon particle size decrease.73 In addition, for most practical potential.75,76 For example, solid emulsifiers containing ioniz-
applications it is desired to be able to recover the stabilizing able groups can change their hydrophilicity with respect to pH.
particles, therefore Levine et al. estimated that the solid particles This phenomenon was explored by Hao et al., where a pH-
should be, at least, one order of magnitude smaller in diameter responsive emulsion system was developed by employing
than the smallest droplets.49 Furthermore, the size-dependent surface active titanium dioxide (TiO2) nanoparticles.77 In the
particle mobility has implications on the final droplet size since, acidic range the particles were fully dispersed in an aqueous
as discussed in the previous section, the equilibrium droplet size phase not being able to form emulsions, which was later made
is influenced by the adsorption time at the interface as opposed possible by increasing the pH value up to 7–8. Ionization of
to the rate of coalescence between the two droplets in the the moieties also affects the particle surface charge and the
continuous phase.64 The droplet size dependency on the particle subsequent electrostatic interactions among them. The impli-
size has been verified experimentally: emulsion droplet size was cations of that effect result in different spacing between the

Fig. 4 Effect of particle size on emulsion formation by sandpack flowing (a) 5 nm, (b) 12 nm, (c) 25 nm, (d) 80 nm (scale bar represents 100 mm), and
(e) average droplet size analysis. Reproduced from ref. 71 with permission from Springer.

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stabilizing particles at the oil–water interface, which subse- wetting properties.102–104 The changes in wettability affect
quently leads to different stability profiles depending on the the adsorption Gibbs free energy making the presence of the
nature of the particle and the pH. particles at the tri-phase boundary layer thermodynamically
The charged nature of nanoparticles used for Pickering unstable.35 As a result, particles tend to redisperse in their
emulsions makes them extremely vulnerable to changes in preferred wetting phases.32 For example, the presence of free
the ionic strength as a consequence of the ion-induced electro- amino groups along the backbone of chitosan turns it into
static shielding effect that reduces their surface potentials a pH-tunable Pickering emulsifier which could adsorb at the
triggering droplet coagulation or flocculation.32,75 This results interface of oil and water to stabilize O/W emulsions.105 At
in reduction of the active surface areas needed for wastewater pH o 6.0, chitosan was soluble in water and did not form
treatment applications limiting the practical use of Pickering emulsions with the oil phase, but when the pH surpassed 6,
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emulsions in samples of high salinity and extreme pH values. chitosan nanoparticles or micrometer-sized floccular precipi-
In these situations, various means of particle modification tates were formed in situ acting as Pickering emulsifiers.105
can be applied to create a protective coating stabilizing the Another study by Low et al.101 reported the dual behavior of
particles from aggregation.33,78,79 The coated particles have Pickering emulsions made of Fe3O4 nanoparticles and poly[2-
been reported to demonstrate enhanced emulsion stability in (dimethylamino) ethyl methacrylate, which could be emulsi-
high salinity conditions owing to the decreased repulsions and fied/demulsified by tuning both the pH and magnetic field.
higher interfacial packing as opposed to the deionized water A similar effect was demonstrated by employing a CO2 sensitive
case.80 Furthermore, numerous papers have demonstrated surfactant, 4-butyl-4-(4-N,N-dimethylbutoxyamine) azobenzene
positive cases where salt was intentionally used in the design bicarbonate, which can be interconverted between the charged
of Pickering emulsions. Li et al. showed that the decrease in and non-charged states with respect to the concentration of
zeta potential induced by added salts for pea protein microgel CO2 dissolved in the water phase. What is more, the molecule is
particles used as Pickering stabilizers would help a hydro- capable of interconverting between cis (more polar) and trans
phobic group to be embedded into the protein curl, resulting (less polar) isomers upon UV or blue light irradiation.95 Both
in a lower hydrophobicity.81 There have also been instances of CO2 and light irradiation are low cost, environmentally benign,
an intentional particle aggregation that would facilitate the and contamination free solutions that could overcome the
migration of particles towards the oil–water interface in order current emulsifier recovery limitations. Yet another example
to improve emulsion stability.82,83 Finally, manipulations of of altering particle wetting properties is by introducing co-
NaCl concentration can induce an emulsion phase inversion surfactants that could adhere to the surface of the stabilizing
and the amount of salt required for that would be dependent particles.106 Alargova et al. argued that the adsorption of a drop-
on the droplet size.84 wise added sodium dodecyl sulfate (SDS) to foams, stabilized by
hydrophobic polymer microrods induced the collapse of the
foam followed by the efficient recovery of the microrods in the
3. Destabilization mechanisms aqueous phase.106 A summary of the aforementioned destabi-
lization mechanisms is depicted in Fig. 5.
The superior stability of Pickering emulsions can be seen as a Although changing the particle wettability covers the majority
disadvantage in most practical wastewater treatment applica- of destabilization mechanisms, one can achieve similar results
tions owing to their recovery limitations.88 The benefits of the by disrupting the packing of the droplets. For example, Vashisth
increased reaction efficacy are often overshadowed by the et al. showed that dodecane-in-water emulsions stabilized by
difficulties in separating and removing the reaction products silica nanoparticles can be demulsified by adding SDS into the
from the biphasic mixtures.88–90 The commonly used catalyst mixture.107 The added surfactant would compete for the oil–
recycling methods such as centrifugation and filtration face water interface by displacing the already existing particles. The
challenges when the particle size approaches sub-micrometer hypothesis was backed by the previously reported results with
range leading to filter blocking, catalyst loss and oxidation proteins being displaced by surfactants due to reduction of the
problems.88–90 Moreover, when it comes to Pickering emul- interfacial tension caused by surfactant adsorption.108 A similar
sions, the demulsification energy barrier lies in the range of 107 phenomenon was later demonstrated by Reynaert et al. where
KBT (KB-Boltzmann constant) making it practically impossible the decane-water interfacial layer stabilized by latex particles was
to achieve.91 Consequently, novel and cost-effective methods characterized with and without SDS present. It was found that
capable of regenerating solid emulsifiers are highly demanded. the presence of SDS disrupted the packing of the latex particles
Various external-stimuli dependent approaches have been making the interfacial particle arrangement looser (more
reported, including the use of pH,61,77,92,93 CO2,86,94,95 open).109
temperature,95,96 magnetic field,97–99 ionic strength,100 or their The key parameters investigated in the previous sections
combinations93,95,101 – some of them will be presented in this will be critical when analyzing Pickering emulsions used for
chapter. wastewater treatment applications. The tunability of PEs makes
In most cases, reversible emulsion breaking is achieved by them very attractive for certain applications, but also difficult to
introducing functional groups on the stabilizing particles that control since many of these parameters are highly inter-
can interconvert between the structures exhibiting different linked.57 All other parameters being identical, different surface

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Fig. 5 Destabilization mechanisms by employing a) variations in pH (reprinted from ref. 77 with permission from Elsevier), (b) magnetic field,85 (c) CO2/
N2 stimulus (reprinted from ref. 86 with permission from Royal Society of Chemistry), (d) temperature differences (reprinted from ref. 87 with permission
from Royal Society of Chemistry).

chemical composition could lead to different surface physico- working mechanisms and the examples demonstrating their
chemical properties, and consequently to different wetting performance in use.
properties and emulsion stability profiles.32,35,36,57 Thus, sys-
tematic studies of independent variables and their implications 4.1 Adsorption
for specific applications are of high interest. The most potent Adsorption is a common industrial method of pollutant
applications will be investigated in the following chapter. removal from wastewaters being particularly effective when
the pollutants are stable against other means of degradation,
i.e., by using aerobic digestion, light, heat, or oxidizing
4. Applications of Pickering emulsions agents.133 Despite the process being rather inexpensive and
for wastewater treatment simplistic, effective separation and regeneration of adsorbents
is still considered a challenge.134,135 Moreover, the eluent must
Pickering emulsions have become ideal candidates for waste- be treated to avoid secondary pollution.136
water treatment owing to their many attractive features, such as To account for these problems, several Pickering emulsions
remarkable stability, tunability, low cost, low toxicity, easy have been designed to act as adsorbents that would overcome
recovery, and high performance due to high interfacial surface the separation and regeneration problem that would otherwise
areas.37,38,98,110,111 Various methods based on Pickering emul- be present in the dispersed case.132,137 A rather simplistic case
sions have been developed for removing contaminants from is depicted in Fig. 6, where the electrostatically-driven adsorp-
wastewater, including adsorption, photocatalytic oxidation, tion of Congo red dye was evaluated by utilizing Ni(OH)2
precipitation, coagulation/flocculation, chemical oxidation, nanosheets as Pickering emulsifiers together with dichloro-
biological processing, or membrane filtration. The adsorption methane as the oil phase.132 The intension was to promote
processes were found to be a special case where the most potent the settling rate of the saturated adsorbent owing to the high
techniques rely on the indirect use of Pickering emulsions density of the oil phase, but the adsorption rate had to be
yielding high performance functional adsorbents. Table 2 sum- accounted for by tuning the droplet sizes such that the adsor-
marizes these applications with the corresponding target bent would not settle before having captured the dye molecules.
pollutants and emulsion architectures listed. Each of these The produced emulsion exhibited a much higher adsorp-
techniques will be further analyzed focusing on both the tion capacity and a faster settling rate compared to Ni(OH)2

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Table 2 Pickering emulsion compositions and their applications in wastewater treatment

Application Modifiers Emulsion type Composition Target pollutant Ref.

Photocatalysis NaF O/W TiO2 Nitrobenzene 62
O/W TiO2 Rhodamine B 112
Hexylamine, continuous flow O/W TiO2 Nile red 113
O/W TiO2 Rhodamine B 111
O/W ZnO Nitrobenzene 114
CNT and graphene W/O Ag3PO4/BiPO4 Acid Blue 92 33
O/W TiO2-rGO MB 115
Catalysis H2O2 mediated, N-doped W/O Janus-CNT 2-Nitrophenol 116
NaBH4 mediated, continuous flow O/W ACNF@Ag 4-NP, MB, MO 117
Adsorption MIPFs W/O Ni(OH)2 nanosheets Rhodamine B 118
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W/O Silica–Oleic acid Lambda-cyhalothrin

MIPFs W/O BA-MSN-PGM luteolin 119
MIPFs O/W silica Bisphenol A 120
PolyHIPEs W/O Fe3O4@humic acid Hg (II) ions 121
PolyHIPEs W/O Poly(4-vinyl pyridine) Plutonium 122
O/W Ag3PO4@palygorskite Tetradecane 123
Coagulation/flocculation Photo-induced polymerization O/W CNC-g-AA-g-CA MB 124
O/W Pt@CdS Phenols 125
Extraction/separation PELM W/O/W Fe3O4 4-Methoxyphenol 97
PELM W/O/W ASNWs Cr (VI) 126
O/W and W/O HBPS-BGE Dimethyl blue/Nile red 87
Biological treatment DVB as pre-polymer complex O/W Fe3O4 + [Link]/P. denitrificans Phenols/DMF 127
PolyHIPEs W/O SRB-Poly(St-MTQ) Sulfates 128
Bactericide Microcapsules O/W CTO/HAp/HACC/SA E. coli and S. aureus 129
Photocatalysis O/W Epoxy acrylate copolymer@ Bacteria 130
nano-TiO2
Steam generation Aerogels O/W CNF/PLA/PANI Salts, organic compounds 131
CNT: carbon nanotubes; rGO: reduced graphene oxide; MB: methylene blue; ACNF: cellulose nanofibers with aldehyde groups; 4-NP:
4-nitrophenol; MO: methyl orange; MIPFs: molecularly imprinted polymer foams; BA-MSN: boronic acid suspended mesoporous silica nano-
particles; PGM: poly(glycidyl methacrylate); polyHIPEs: polymers from high internal phase emulsions; CNC-g-AA-g-CA: cellulose nanocrystals-
ascorbic acid- citric acid; PELM: Pickering emulsion liquid membrane; ASNWs: amphiphilic silica nanowires; HBPS-BGE: 2-hydroxy-3-butoxypropyl
starch with butyl glycidyl ether; [Link]: Pseudomonas putida; [Link]: Paracoccus denitrificans; SRB: sulfate reducing bacteria; St-MTQ:
styrene-MTQ silicone resin; CTO/HAp/HACC/SA: citronella oil loaded microcapsules with hydroxyapatite /quaternary ammonium salt of chitosan/
sodium alginate; CNF/PLA/PANI: cellulose nanofibril/polylactic acid/polyaniline.

Fig. 6 Preparation process of Ni(OH)2 nanosheet stabilized Pickering emulsion with the electrostatic adsorption mechanism depicted. Reprinted
from132 with permission from Elsevier.

dispersed in the water phase. The difference was explained by sites for adsorption as opposed to the ordered emulsion
the embedding effect between the bare nanosheets during structure. More examples include iron oxide-modified magne-
deposition, which would effectively reduce the number of active tically separable emulsions targeting rhodamine B (RhB)138 or

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layered hexaniobate emulsions, capable of adsorbing both through a facile Pickering emulsion polymerization using silica
water-soluble and lipophilic dyes.139 nanoparticles.120
Although direct adsorption systems have been known, When it comes to removal of heavy metal ions, adsorbents
their complexity and performance limitations did not lead to must possess a hydrophilic character.140 Several ways of intro-
further attempts to commercialize the process. However, the ducing hydrophilic moieties have been proposed, but the most
most prominent adsorbents are generally made by applying prevalent one is the post-synthesis modification of hydropho-
Pickering emulsions indirectly.137,140 The functional porous bic polyHIPEs. Mert et al. formulated styrene/divinylbenzene
materials made by templating Pickering emulsions have gained (ST/DVB) based polyHIPEs stabilized by humic acid-modified
considerable attention owing to their tunable porous structure, oxide magnetic nanoparticles (Fe3O4@HA) that showed a high
surface properties and high specific surface area.140 The main adsorptive capacity for Hg(II) ions.121 Another approach was
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group of highly porous adsorbents based on Pickering emul- realized by Pribyl et al., where polyHIPE foams were surface-
sions are so-called polyHIPEs: polymeric high internal phase grafted with a brush of a polymer containing ion-exchange sites
emulsions (Fig. 7).141 This type of materials has already demon- designed to remove plutonium.122 The post-modified poly-
strated potential for removal of heavy metal ions,142 organic HIPEs strategy although being quite effective, remains tedious
contaminants (i.e., dyes, surfactants, pesticides) and for oil and costly to be produced on a large scale.140 Due to this
spilling.140 reason, there has been an increasing interest in O/W polyHIPEs
A vast number of different adsorbents has been fabricated as opposed to conventional W/O systems, which require
by utilizing Pickering emulsions as precursors relying on the post-modification.141 For instance, a series of magnetic O/W
polyHIPEs technology.140 Pan et al. used a common pesticide polyHIPEs were prepared through a free-radical grafting poly-
l-cyhalothrin in the continuous phase coupled with the poly- merization method by immobilizing surface-modified iron
merizable PEs to synthesize polyHIPEs with an enhanced oxide nanoparticles.143 The subsequent grafting of acrylic acid
recognition towards the pollutant.118 The adsorption results onto hydroxypropyl cellulose tailored the specific adsorp-
indicated favorable adsorption kinetics and high adsorption tion sites towards Rb+ and Cs+ ions. Furthermore, the use of
selectivity. Similarly, a cis-diol specific adsorbent system can be stabilizing magnetic nanoparticles is extremely advantageous
designed by functionalizing silica NPs with boronic acids, for adsorbent recovery. Finally, tunability of the pore geometry,
which are known for their affinity towards the formation of simplicity of the synthesis and versatility towards a wide range
complex compounds with carbohydrates.119 Another study of ions metal ions makes the polyHIPEs technology very attrac-
showed that bisphenol A could be selectively adsorbed by synthe- tive for advanced adsorbent development. There is, however, a
sizing molecularly imprinted multicore rattle-type microspheres theoretical Pickering emulsion porosity limitation of 74.048%

Fig. 7 Fabrication steps of the Polymerized High Internal Phase Emulsion (PolyHIPE). (a and b) The gradual addition of the internal phase into the
continuous phase while the system is mixed, (c) polymerization of the high internal phase emulsion (HIPE), (d) 2D projection of PolyHIPE, (e–g) the
formation of the pores and windows, and (h) scanning electron microscopy image.141

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dictated by the highest possible dispersive phase volume.141 liquid membrane separating the two miscible phases. Therefore,
In order to surpass this limit and further enhance the adsorp- ELM based extraction systems can be thought as equivalent to
tion capacity, multi-hollow structures in the polymer micro- double emulsions that exist as W/O/W (water-in-oil-in-water) and
spheres or double emulsion systems can be fabricated. In these O/W/O (oil-in-water-in-oil).151 The separation is achieved by
systems droplets of the dispersed phase themselves contain transporting species across the oil phase so that they would be
even smaller droplets.144 trapped inside the internal aqueous phase. The W/O emulsion
can afterwards be broken up through various stimuli to release
4.2. Coagulation/flocculation the contents of the internal phase. Despite the appealing
concept, commercialization of ELM has been limited due to
Typical inorganic or synthetic wastewater treatment flocculants
instability of emulsions and the difficulty of demulsification
despite being highly effective and relatively cheap, lack bio-
after extraction.148,149
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degradability hence cause secondary pollution to the environ-

Adaptation of an ELM template to Pickering emulsions has
ment.145 Other drawbacks include a large amount required for
been found to be an option that would circumvent the main
efficient flocculation, high sensitivity to pH, inefficiency
drawbacks of a typical ELM system. Pickering emulsion liquid
towards very fine particles, and applicability only to selected
membrane (PELM) concept replaces surfactants used in ELM
disperse systems.145,146
with solid nanoparticles that provide higher emulsion stability
The carboxylated cellulose nanocrystals (CNCs) can address
and easier demulsification owing to their wide range of particle
these challenges by utilizing their strong electrostatic adsorp-
functionalization pathways152 (Fig. 8). Only a handful of studies
tion between anionic carboxyl groups and cationic dyes or
so far considered using PELMs for wastewater treatment most
suspended particles that would in turn exert strong enough
notably by using magnetic particles as emulsifiers.97,147 One
attractive forces to overcome the electrostatic repulsion.124
instance of a PELM-like system was demonstrated by using
Kaolin suspension (wastewater model system) was coagulated
Fe2O3 particles as co-emulsifiers in ELMs to characterize the
by forming O/W Pickering emulsions, stabilized by CNCs with a
stability and efficiency in extracting lead ions (Pb2+) from
variable carboxylic group density. It was found that indeed,
aqueous solutions. The method was proven to be useful for
more anionic groups on the CNC surfaces enhanced the
improving the membrane stability (emulsion breakage as low
electrostatic adsorption due to charge neutralization leading
as 0.3%) with Pb2+ extraction efficacy up to 97.2%.152 Alterna-
to a more effective turbidity reduction.
tively, Lin et al. made use of a nano-Fe3O4 PELM system that
Alternatively, a new reaction system for the simultaneous
could extract over 86% of 4-methoxyphenol (4-MP) from
removal of aromatic contaminants from wastewater was
wastewater.97 The working mechanism of extraction is depicted
demonstrated by carrying out a photo-induced oxidative poly-
in Fig. 9: 4-MP in the feed phase diffuses to the O/W interface
merization of phenolic substrates via a chain growth mecha-
of the membrane and reacts with the tri-n-butyl phosphate
nism, thereby providing a path for pretreating water by
(TBP) carrier capable of forming an oil-soluble complex with
flocculating out contaminants with a concurrent generation of
4-MP. The complex then diffuses across the oil phase of the
hydrogen.125 The propagating polymer chain would exhibit a
membrane to reach the internal W/O interface, where it forms a
decreasing water-solubility pattern with each added monomer
salt which cannot diffuse back into the oil phase. As a result,
up to a point, where a poly-phenolic Pickering emulsion from
4-MP is selectively extracted by the carrier from the external
the contaminants originally found in wastewater could be
feed phase to the internal phase. The system can then be
formed. Additionally, the reaction results in generation of
hydrogen gas, which can be utilized as a useful byproduct.
Further development is still needed to replace the currently
used Pt@CdS substrate with particles composed of less toxic
and more earth abundant materials to make the system viable
for water cleaning.

4.3. Extraction/separation
Methods like microfiltration, ultrafiltration, and reverse osmosis
are very well established in the wastewater treatment process,
but the limitations such as low efficiency, difficult operating
conditions and high maintenance costs create an interest for
alternative solutions.37 Emulsion liquid membranes (ELMs) have
recently emerged as potential substitutes used in separation and
extraction processes owing to their simplicity, high selectivity,
rapid extraction, and low energy consumption.148–150 ELM tech-
nology typically relies on a conventional W/O surfactant-
stabilized emulsion dispersed in an external feed phase, which Fig. 8 Extraction mechanism of a PELM system. Reprinted from ref. 147
is usually aqueous.37 The oil phase is then considered to be the with permission from Elsevier.

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4.4. Photocatalysis
Over the last few decades, there has been a great interest in
developing photocatalysts with high catalytic efficiency and
good stability towards common pollutants in industrial waste
waters around the globe.153 The evolution of advanced oxida-
tion processes (AOPs) has drawn attention towards the photo-
catalytic means of generating radical species, which would then
unselectively decompose organic pollutants making the con-
taminants be quickly and efficiently fragmented and converted
into small inorganic and organic molecules.154 Even though the
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formation of highly oxidizing active oxygen species through

Fig. 9 Schematic diagram of 4-MP extraction by PELM technology. light induced redox reactions allows degradation of almost
Reprinted from ref. 97 with permission from Elsevier.
every organic substrate, its full potential has not been reached
yet.62 For example, the efficiency of photocatalysis drops as the
contaminant concentration drops155 or if hydrophobic organic
demulsified by applying magnetic field or centrifugation. pollutants poorly adsorb onto the hydrophilic surface of the
In fact, the proven efficacy of centrifugation as a feasible photocatalyst making the reaction kinetically hindered.156
destabilization route facilitates the expansion of emulsifiers In general, the photocatalytic efficacy is highly dictated by the
beyond magnetic particles. interfacial phenomena, therefore enhancing the contact area
One example of non-magnetic PELMs by Perumal et al.126 between contaminants and photocatalysts would be an effective
indicated that amphiphilic silica nanowires (ASNWs) can be route to improve the photocatalytic activity.114
used as PELM surfactants for extraction of Cr6+ ions. The Considering these challenges, the benefits associated with
prepared PELM was very effective in the extraction of chromium the photocatalytic nanoparticles become obvious owing to their
at lower concentrations although lacked the means of recovery. large catalytically active surface areas, broadening of the band
ASNWs were also reported to be suitable for the removal of both gap and faster spatial charge-transfer.157 These assumptions
Cu2+ and Cd2+ indicating a superior performance compared to were confirmed by Koci et al., where a clear nanoparticle size
alumina or sorbitane monooleate (SPAN 80). Regardless of dependency was observed – as the particles got smaller, both
being in the early phase of development, PELM technology the charge-carrier dynamics and light absorption efficiency
shows a high potential for becoming a viable extraction tech- of TiO2 nanoparticles improved, leading to an exponential
nique used in wastewater treatment. increase in the catalytic activity.158 An elegant way to reduce
Aside from liquid membranes used for pollutant separation, droplet sizes and enhance the contact between photocatalysts
a new group of super wettable materials has emerged addres- and pollutants is by employing Pickering emulsions, which rely
sing the drawbacks of conventional techniques, such as gravity on the solid photocatalyst particles as emulsion stabilizers.
separation, skimming, and flotation.87 A major industrial chal- The system is then composed of small and stable nanoparti-
lenge is the effectiveness of emulsion separation, which can be cles surrounding hydrophobic droplets – a matrix made of
targeted by utilizing extreme values of wettability thus provid- photocatalytic micro-reactors, that can be recoverable by
ing excellent material properties for the separation of different demulsification.36,62,159 The advantages deriving from the use
water–oil mixtures.87,140 Thermoresponsive 2-hydroxy-3- of stable, cheap, and abundant nanoparticles combined with
butoxypropyl starch (HBPS) was produced and later surface- the increased photocatalytic activity show a high potential in
modified by Pickering emulsion polymerization to produce developing universal methods for effective degradation of
super wettable porous spheres used for oil/water separation.87 organic pollutants in wastewater through photocatalysis.36
By changing the temperature, one could emulsify (below the Pickering emulsions have shown promising results as
lower critical solution temperature (LCST) and demulsify photocatalytic systems for the degradation of organic contami-
(above LCST) oil/water mixtures by exploiting changes in poly- nants in wastewater treatment. A classical example of the
mer wettability with respect to temperature. The polymer superior PE performance over the dispersed particle system
spheres would then serve as a porous layer for separation: was presented by Fessi et al., where 1-methylnaphthalene-
during the separation of stable water-in-oil emulsions, the oil (1-MN) was exploited both as an oil phase and as a target
phase would freely pass through the layered spheres, whereas pollutant.62 In this case, the water dispersed bare TiO2 nano-
the water droplets would be repelled. Conversely, the dispersed particles would adsorb on the surface of the pollutant droplets
oil phase in oil-in-water emulsions would be adsorbed by the acting as small microreactors with an enhanced contact area
polymer spheres forming a thick layer that could only be and photodegradation efficacy.62 The degradation rate was
penetrated by water when a vacuum pump is used. According compared between the blank (TiO2 free), non-emulsified and
to the initial results indicating the separation efficiency of emulsified conditions in the presence of TiO2. It was found that
99.9%, it is believed that super wettable materials could around 95% of (1-MN) could be degraded after 24 h of UV
become the future state-of-the-art technology used in separa- irradiation, compared with only 25% in the non-emulsified
tion of complex fluids.87 system. Substantial research is also done on the water-soluble

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dye removal from the wastewaters containing Nile red, Methy- Regarding the combined adsorption-photocatalysis approach,
lene blue and Rhodamine B.111–113 A very interesting case was X. Zhang et al. fabricated amphiphilic graphitic carbon nitride
presented by Q. Li et al., where the wetting of bare TiO2 (g-C3N4) to degrade rhodamine B (RhB) dye from wastewaters
particles was in situ tuned by the adsorbing sulfonate groups (Fig. 11).111 The dye molecules could be captured by g-C3N4
from the reactive brilliant red (X3B) molecules (Fig. 10a).38 acting as a Pickering emulsifier-adsorbent, which would
The adsorbed pollutants reduced the hydrophilicity of bare simultaneously photodegrade RhB upon irradiation. The pro-
titania, thus empowering titania to be an emulsifier capable of cess does not require any stirring or secondary treatment,
forming stable emulsions between water and dichloromethane. which are needed in conventional wastewater treatment
The prepared Pickering emulsions would then undergo a photo- processes. Under visible light irradiation, the conversion of
catalytic decomposition of titania-coated sulfonate-carrying RhB removal reached 100% within 25 min and the used
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pollutants, which would gradually demulsify the system provi- PEs could be reused without any reduction in performance.
ding excellent recyclability for reuse after irradiation (Fig. 10b). Another example was shown by preparing a composite made of
As an alternative to TiO2, Wu et al. proved that the modi- highly absorbent palygorskite (PAL) clay particles and silver
fied zinc oxide (ZnO) nanoparticles are perfectly feasible for phosphate (Ag3PO4), which is a common photocatalyst.123
photocatalytic applications of organic contaminants in waste- The targeted removal of tetradecane indicated a 4.9 times
waters.114 higher efficiency compared to Ag3PO4 particles alone. Adsorp-
Photocatalytic applications involving PEs are not just lim- tion also played a big role in enhancing the photocatalytic
ited to the use of metal-oxide emulsifiers – complex compounds degradation of TiO2–graphene oxide composite towards methy-
have been made with superior properties compared to conven- lene blue.115 Many mesoporous voids acting as adsorption
tional materials used for Pickering emulsions. One famous chambers were created by growing TiO2 nanoparticles on
example has been demonstrated by Mohaghegh et al.,33 where the interface of O/W type GO Pickering emulsions. Overall,
a novel p–n junction Ag3PO4/BiPO4-based Pickering emulsion the combined strategy has been proven to be highly effective
coupled with either graphene or hydrophobic multi-walled due to the individual contributions of the components consti-
carbon nanotubes was formed. The measured Acid Blue 92 tuting the composites.
dye degradation with respect to irradiation time indicated a The overall strategy of bridging advances in the research of
highly effective photocatalytic activity far superior to the dis- photocatalytic Pickering emulsions is defined by two main
persed control case. The improvement was attributed to an paths of development: improving photocatalyst performance
enhanced migration of the produced O2, which is more soluble to meet industrial requirements or enhancing the mass transfer
in the oil phase than in water. The self-induced removal of the of low-concentration pollutants to intensify the process.160–162
product shifted the equilibrium to the product formation side Although the former has been studied quite extensively in
thus improving the rate of pollutant degradation. More studies recent years, a substantial pollutant degradation process takes
have been done by using graphene oxide (GO) and its compo- place in the order of hours, which is too long to be implemen-
sites by exploiting the benefits of highly efficient electron ted in industry.111 Nevertheless, recent success in pursuing the
transfer and smooth connection between materials hence mass transfer route opened new possibilities for the enhanced
improving the photocatalytic degradation performance.115 photocatalytic timescales.160,163,164

Fig. 10 (a) Schematic of an o/w Pickering emulsion formation from super hydrophilic TiO2 coated with sulfonate-carrying pollutants for photocatalytic
dye degradation testing, (b) four photocatalytic cycles of reactive brilliant red (X3B) degradation in the PE system with the same catalysts recovered.
Reprinted from ref. 38 with permission from Elsevier.

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Fig. 11 Schematic of coupling process of adsorption, extraction, and photocatalysis. Reprinted from ref. 111 with permission from Elsevier.

4.5. Biological treatment before the polymerization providing a pathway for the bacteria–
Among the pool of industrial methods used to remove soluble polymer composites to be separated by magnetic field. The
organic pollutants from wastewater, the biological treatment pollutant removal profile is illustrated in Fig. 12b: sharp
techniques are known to be the most cost-effective.7,165,166 reduction in DMF concentration is initially attributed to adsorp-
These methods can withstand a wide range of concentrations, tion followed by biodegradation by the MPB ultimately reaching
produce harmless species, and show a high removal efficiency.167–169 negligible values in concentration. The removal of phenols
Immobilized microorganism technology has recently emerged followed a very similar trend to the removal of DMF as discussed
as a feasible water treatment alternative offering advantages, such above. Not only could the final composite effectively adsorb and
as high cell density, easy recovery, high microbial stability, and remove organics from the aqueous solutions, but the magnetic
the possibility to run the process continuously.170 As a result, separability also made the system fully reusable with no second-
numerous groups have evaluated the use of natural and artifi- ary pollution created. The same principle was later applied in
cial microbial supports in bioreactors.171–173 One potent fabricating bacteria-immobilized Pickering emulsions for desul-
research branch focusing on biomass immobilization makes furization and oil-removal.128,174
use of Pickering emulsions acting as multifunctional substrates
enabling effective adsorption, separation, and biological degra- 4.6. Other applications: steam generation, catalysis,
dation of wastewater pollutants. For example, Cai et al. bactericide
covalently immobilized two types of bacterial cells (Pseudomonas Having defined the main development areas of Pickering
putida and Paracoccus denitrificans) on the surface of func- emulsions in wastewater treatment applications, one could
tional polymer particles to effectively degrade phenols and analyze alternative ideas deepening our knowledge and expos-
N,N-dimethylformamide (DMF) as model systems (Fig. 12a).127 ing new principles that can later be incorporated into the most
Additionally, iron oxide nanoparticles were added to the oil phase potent pollutant degradation techniques.

Fig. 12 (a) Schematic illustration of the preparation and structure of the magnetic bacteria–polymer (MPB) composite, (b) the adsorption-
biodegradation process of DMF by MPB. Reprinted from ref. 127 with permission from Royal Society of Chemistry.

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Pickering emulsions have become universal templates in acid/polyaniline (CNF/PLA/PANI) hybrid aerogel as a self-
particle engineering that can be utilized in the production of floating photothermal device for solar steam generation (Fig. 13a).
bactericidal materials, such as composites, microcapsules, or The evaporation was carried out under the irradiation of 1 sun
porous scaffolds. For instance, citronella oil (CTO), a well- with the aerogel maintaining temperatures up to 105 1C, which
known antibacterial agent,175 was loaded to produce composite resulted in an evaporation rate up to 1.58 kg m 2 h 1. Overall,
microcapsules with hydroxyapatite (HAp)/quaternary ammo- the aerogel exhibited an excellent performance durability and
nium salt of chitosan (HACC) and sodium alginate (SA) shells structural integrity over the multiple cycles it was used. The
in pursuit to inhibit E. coli and S. aureus growth used as model experiments carried out on 3 wt% mixed salt solutions indi-
bacteria found in wastewaters. The fabrication was performed cated a noticeable reduction in the concentrations of Na+, K+,
under ambient conditions without the use of surfactants and Ca2+, and Mg2+ making the purified water compliant with the
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with the composites exhibiting excellent thermal stability. The WHO safe drinking water standard and the US Environmental
prepared microcapsules showed a sustained release activity and Protection Agency (EPA) standard (Fig. 13b).177 The same
displayed a significant bacterial inhibition effect.129 An alter- principle can be further expanded into organic pollutant
native particle design targeting antibacterial activity towards removal: the absorption peaks at 464 and 550 nm corres-
E. coli and S. aureus was realized by making grafted xanthan ponding to water contaminated with methyl orange and rho-
gum with poly(vinylimidazole) (XG-g-PVI) nanocomposites in damine B, respectively, disappeared after collecting the purified
the presence of different Montmorillonite (MMT) nanoclays.176 water. These observations confirmed high purification ability of
MMT is known for its charged layer structure making it a great CNF/PLA/ PANI aerogels towards a wide range of pollutants in
adsorbent for contamination removal in wastewaters. What is wastewater.
more, the cross-linked nanocomposites made of antibacterial Finally, despite the photocatalytic route for organic pollu-
thermally stable synthetic polymers such as poly(vinylimid- tant degradation being regarded as the leading catalytic
azole) (PVI) with XG would furthermore enhance the mechan- approach, other types of catalytic reactions can be just as useful
ical strength and adsorption efficacy of the resulting structure. to exploit. Janus-like amphiphilic carbon nanotubes (CNTs)
Lastly, the photocatalytic properties of TiO2 were exploited to were tested as catalysts in the oxidation of 2-nitrophenol
synthesize antibacterial epoxy acrylate copolymer@nano-TiO2 (2-NP) with hydrogen peroxide.116 The reaction would take
composite particles (PkE@NT) by carrying out Pickering emul- place at the biphasic oil–water interface, where 2-NP would
sion polymerization.130 Apart from the antibacterial properties, be continuously fed from the oil phase due to the disappear-
the resulting emulsion demonstrated high adhesion and water ance of it in the aqueous phase. Similarly, Ag-decorated cellu-
absorption properties making them suitable for waterborne lose nanofibers (ACNF@Ag) were used as Pickering emulsifiers
antibacterial and humidity controlling interior coatings. to demonstrate the feasibility of continuous flow catalysis by
The generic approach of introducing bactericidal species into reducing organic pollutants (4-nitrophenol (4-NP), methylene
Pickering emulsions provides unique opportunities for envir- blue (MB), and methyl orange (MO)) with sodium borohydride
onmentally friendly and energy-efficient wastewater treatment (NaBH4).117 Very high conversion rates were obtained for 4-NP
applications. (498%, 50 h), MB (499%, 30 h), and MO (496%, 40 h). This
A novel water evaporation-based technology was displayed example illustrates the potential of Pickering emulsion-based
by S. Li et al.,131 where Pickering emulsions were used to continuous flow approach as a viable framework for other
synthesize a light absorbing cellulose nanofibril/polylactic means of industrial wastewater treatment solutions.

Fig. 13 (a) Working mechanism of CNF/PLA/PANI aerogel assisted water treatment, (b) ion concentration change before and after desalination
Reprinted with permission from ref. 131. Copyright 2020 American Chemical Society.

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5. Pickering emulsions in flow disappearing with the renewal of the continuous case, whereas
the emulsion droplets were sufficiently buoyant to maintain
The majority of applications presented in this review have been the lower portion of the reactor effectively nanoparticle free.
based upon wastewater treatment under batch operation, As predicted, the collected outlet stream contained only
which is not the preferred mode of operation for industrial reaction products, and enabled steady-state operation with no
applications.178 The product separation and emulsion regen- detectable loss of photocatalyst. The study illustrates the sta-
eration challenges are often tackled with advanced particle
bility and scalability of the process aiming to reduce the costs
engineering techniques, which are cost inefficient. Having a
and complexity of the most state-of-the-art solutions being
continuous flow system would remove the need for sophisti-
published. Several other reports on the PE stability, droplet
cated materials, increase the conversion, selectivities and sim-
sizes and catalytic performance under continuous flow have
plify the product separation by enabling the collection of the
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been published in the recent years, but its full potential has not
treated water at the outlet of the reactor.113 Furthermore,
been fully explored yet.29,164,181,182
focusing on mass-transfer limitations is becoming a more
effective route in Pickering emulsion development for targeted
applications.113,179,180
A pioneering work was done by Burdyny et al. demonstrating 6. Outlook
the enhanced photocatalytic performance in flow by titania
stabilized Pickering emulsions.113 Initially, the degradation of There has been a breakthrough in the last couple of decades in
methylene blue under batch conditions was tested to compare terms of the research effort put into developing functional
the dispersed and emulsified systems both yielding similar materials based on Pickering emulsions. The emulsions can
reaction rates (Fig. 14a and b). Then, the same conditions were nowadays be synthesized in various forms and shapes ranging
tested in continuous operation indicating a large difference from simplistic O/W emulsions with spherical particles to
between the dispersed and emulsified systems (Fig. 12c and d). microbowl-stabilized double emulsions. The original purpose
It was later discovered that the dispersed particles were of these emulsions has also been changing from the direct

Fig. 14 Comparison of an oil-in-water SNPR with a dispersed aqueous nanoparticle suspension under batch and continuous operation. (a) Schematics
of methylene blue degradation in a well stirred (fully dispersed) batch reactor using aqueous and emulsion-based photocatalysts. (b) Dye degradation
over time for both fully dispersed batch reactors. (c) Schematics of methylene blue degradation in continuous reactors with aqueous and emulsion-
based photocatalysts. (d) Comparison of the percentage of methylene blue degraded over time for each reactor with a continuous inlet flow of 60 mL h 1
of 4 mM methylene blue. Reprinted from ref. 113 with permission from Royal Society of Chemistry.

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usage to well-defined framework structures used for subse- 7. Conclusions

quent polymerization and fabrication of novel materials.
With the rise of potential uses of Pickering emulsions, many Pickering emulsions have emerged as a versatile framework
studies are now focused on optimizing the current PE systems used for the preparation of functional materials suitable for
by improving the emulsion stability and tailoring the functional various means of wastewater treatment. The unique features
properties for a cost-effective and easily scalable solution in an such as high surface area, stability, easy production and tun-
industrial setting. Understanding the influence of key descrip- ability make them very attractive as precursors in applications
tors such as particle wettability, concentration or oil/water alternative to traditional methods that often suffer from per-
volume fraction is crucial for the development of novel waste- formance and recovery limitations. Despite the individual
water treatment systems that could compete with the conven- challenges, the extrapolated benefits each method could bring
on an industrial scale puts this field at the forefront of research
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tionally used methods. Besides, there is still enough room for

fabricating novel materials with interesting properties and interest.
morphologies. For example, only a few examples exist with The primary objective in fabricating these materials has
Janus particles, which could combine several pollutant degra- been identified to be the ability to form stable emulsions,
dation techniques together. Another interesting field is the use which is a challenge on its own due to a highly interlinked
of organic and bioparticles to stabilize emulsions: some bio- nature of the critical emulsion stability parameters. Analysis of
particles (e.g., starch) have already been reported to act as these parameters enlightened the importance of particle wett-
Pickering emulsifiers. While the conventional surfactants for ability, morphology, oil/water volume fraction, concentration,
emulsions stability are efficient, it is necessary to phase them size, shape, the ionic strength, and the pH opening wide
out to reduce volatile organic compounds and carbon foot- opportunities for tuning the emulsions type, droplet sizes and
prints. Incorporating these particles into wastewater treatment their stability. A wide range of demulsification methods has
processes would eliminate the need for sophisticated particle been presented resulting from surface functionalization of
recovery steps as well as provide a cheap, bio-friendly, and solid particles. These methods serve as a basis for reusability
simplistic alternative. and efficient particle recovery.
More fundamental studies on emulsion stability could help Given the progress made in the development of Pickering
to assess the impacts of varying particle shape and morphology emulsions, more studies are needed on the optimization of the
since most studies rely on the behavior described for spherical developed methods aiming to create cost-effective and easily
particles. This research could be extended to mass transfer scalable systems offering advantages over the conventionally
effects, which are becoming more important with the approach- used wastewater treatment techniques. The increased knowl-
ing limits of particle efficacy. A comprehensive analysis of edge of Pickering emulsions and their applications is expected
packing effects and their implications on pollutant mass trans- to promote their use in industry.
fer across the particle-stabilized interfaces could help to design
effective Pickering emulsion systems. Conflicts of interest
Regarding the individual applications, much effort has
been made to develop porous adsorbents based on the poly- The authors declare that the research was conducted in the
HIPEs technology as well as the photocatalytic PEs focused absence of any commercial or financial relationships that could
on pollutant degradation in wastewaters. Despite the progress, be construed as a potential conflict of interest.
there are still many technological and economic obstacles
that impede the transition from the laboratory scale to indus- Acknowledgements
try as the proposed techniques are generally too costly
and complex for upscaling. The photocatalytic route, for The authors gratefully acknowledge the PhD grant (Z. G.) by
instance, could be improved in terms of the light absorption The Particle Engineering Centre at department of Chemical
ranges, reusability, and the costs of material production. Engineering. Furthermore, a deepest gratitude is expressed
Similar trends exist for other applications, where cost- to Sebastien Charles Simon for the fruitful discussions and
effectiveness remains a challenge even though the mechanism critical views on the subject.
of action is much more efficient compared to the currently
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