c05

157
Self-Healing Materials for Environmental Applications
5.1 Biomimetic Self-Healing Materials

Biological materials from plants and animals always exhibit their optimized
functional systems during the process of evolution. One of the most amazing
performances is self-healing capability of restoring health and soundness of
a system and regenerating the tissue structure and functions when damaged
by external forces. In all plants and animals, firstly, a self-sealing phase and,
secondly, a self-healing phase can be identified. The rapid self-sealing prevents
from infection by germs and gives time for the subsequent self-healing of
the injury, resulting in wound closure and the organ restoration. The scale of
biological self-healing can range from molecule level such as the restore of DNA
to macroscopic level like the union of the fractured bones. In addition, for the
biological materials, they can heal the damaged surface functional components
by re-secretion of relevant chemical substances.
Biological materials provide a great inspiration for scientists and engineers to
make bio-inspired artificial materials that can heal themselves when damaged
[1]. Recently, inspired by inherent regeneration capability of biological materials
under external damage, more and more artificial materials have been designed
by integrating self-healing properties with mechanical/electrical/chemical
functions, which are beneficial for long-term use and improving maintenance,
reliability, and durability in their practical application. The introduction of
self-healing ability can effectively cut down the replacement cost of some easily
worn materials with high price by healing the materials instead of replacing them.
Self-healing materials avoid the original degradation through the initiation of a
repair mechanism in response to the micro-damage. It is thus undisputed that
self-healing capability provides the man-made materials enormous possibilities,
in particular for applications where long-term reliability in poorly accessible
areas is important.
In such a concept, a wide range of intelligent self-healing materials with mul-
tifunctions has been developed and explored in diverse scientific areas such as
biomedical materials, smart wearable electric devices, environmental applica-
tion, etc. [1–6].
Artificially Intelligent Nanomaterials for Environmental Engineering, First Edition.

Peng Wang, Jian Chang, and Lianbin Zhang.
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2019 by Wiley-VCH Verlag GmbH & Co. KGaA.
158 5 Self-Healing Materials for Environmental Applications
5.2 Overview of Self-Healing Materials

Early in ancient time, the Romans used a form of lime mortar that was found
to possess self-healing performance. Self-healing materials can be traced in the
1970s. A hard elastic polypropylene was observed to be capable of healing inter-
lamellar microvoids, which were formed after stretching in the perpendicular
direction [7, 8]. However, self-healing materials were widely recognized and stud-
ied in the scientific area until the twenty-first century. The initial overview of
self-healing materials gradually covered the entire spectrum of materials from
polymers to metals and ceramics.
In general, self-healing materials could be widely defined as an artificially or
synthetically created intelligent substance, which can spontaneously repair dam-
age by themselves without any external diagnosis of the problem or human inter-
vention. Hence the occurrence of damage can be also seen as a trigger to initiate
the generation of healing agents toward damage sites, leading to the directed mass
transport for filling the defect and the subsequent mending reaction by physical
interaction or chemical bonding. In the self-healing process, the healing agents
filled into damage sites and gradually became stable and immobilized to guaran-
tee perfect recover of original properties with the healed structures or chemical
composition.
Resembling biological systems, an ideal self-healing is automatically triggered
only by damage. Namely, the damage itself can be applied as a stimulus for the
self-healing process. It is mainly based on the intrinsic structure and compo-
sition of materials with the ability of detecting the damage and synchronous
self-healing. However, in most of the self-healing systems, external stimuli other
than the trigger of damage are generally applied to initiate the movement of
the healing agent toward damage sites. The typical external stimuli include
heat [9–12], pH [13–15], light [16–22], redox [23, 24], electrical field [25, 26],
magnetic field [27], etc.
In terms of self-healing materials, although inorganic materials such as metals
and ceramics have been also used in the construction industry as a healing agent
to heal physically structural cracks of materials [28], their diffusive mass transport
toward damage sites is always activated by high temperatures (>600 ∘ C for metals
and >800 ∘ C for ceramics) [1], due to the fact that their solute atoms as heal-
ing agents are relatively tiny and possess a relatively low mobility at the prevail-
ing operating temperatures, which limits their application breadth. In contrast,
polymer chains can be more readily mobile for self-healing at low temperature
(<120 ∘ C) [1]. Nowadays, self-healing polymeric materials attract much more
attention than inorganic ones due to their lightweight, wide availability, flexibility,
easy processing and manipulation, etc. [29]. This is especially true in environmen-
tal processes. Hence, in this chapter, we mainly discuss the polymeric self-healing
materials in environmental applications, as well as their chemical mechanism and
self-healing modes behind.
5.3 Extrinsic and Intrinsic Self-Healing Materials 159
5.3 Extrinsic and Intrinsic Self-Healing Materials

To be more convenient to discuss the design and fundamental mechanism of
self-healing materials, the self-healing materials are categorized into two types:
extrinsic and intrinsic self-healing materials [1, 30, 31], depending on the source
of self-healing agents.
5.3.1 Extrinsic Self-Healing Materials

Extrinsic self-healing materials do not have self-healing capability in the matrix.
They have external healing agents embedded across the entire host matrix mate-
rials in the form of micro/nanocapsules or vascular networks [1, 32, 33].
When the damage occurs, the embedded capsules or vascular networks break
to release the healing agents, then heal the matrix materials based on the healing
agents’ polymerization reactions, and prevent damage propagation.
In general, encapsulation of healing agents could be carried out by various
methods including in situ polymerization, interfacial polymerization, internal
phase separation, and solvent evaporation technique [34]. Typically, various
capsule shells could be synthesized through abovementioned techniques, such
as urea–formaldehyde (UF) resin, melamine formaldehyde (MF), polyurea
(PU), poly(methyl methacrylate) (PMMA), etc. [35–40]. Correspondingly, dicy-
clopentadiene (DCPD), polydimethylsiloxane (PDMS), glycidyl methacrylate,
epoxy resins, isocyanates, linseed oil, aliphatic amines, and so forth are typically
selected as healing agents and microencapsulated [38, 41–43]. Among them,
some kinds of isocyanates, such as isophorone diisocyanate (IPDI), hexam-
ethylene diisocyanate (HDI), polyaryl polymethylene isocyanates (PAPI), etc.
[44–48], can react with moisture and are being used as potential healing agents
to create catalyst-free self-healing materials in moist or aqueous environments.
In 2001, White et al. firstly reported extrinsically structural self-healing mate-
rials that could automatically heal cracks by incorporating a microencapsulated
healing agent (Figure 5.1a) [32]. The microencapsulated self-healing agents
(DCPD monomer) could be released after damage, and the released agents could
intrude into the crack plane through capillary action and then contact with
an embedded Ruthenium-based Grubbs’ catalyst in the matrix to trigger the
ring-opening metathesis polymerization and heal the crack faces.
Although the capsule-based healing concept has been commonly employed
owing to simple fabrication, the inherent drawback of microcapsule-based
self-healing materials restricts their practical application, stemming from the
local healing agent’s depletion after a single damage event [33].
Based on this challenge, Sottos and coworkers (Figure 5.1b) further developed
the bio-inspired vascular self-healing systems [49], where a three-dimensional
interpenetrating microvascular network was embedded into the substrate.
When physical damages occur, the healing agent inside networks could be
Cut
Epidermis
Capillaries
sels
Dermis d ves
r bloo
Large
(b)
(a) (c)
Figure 5.1 (a) Capsule-based healing concept. A microencapsulated healing agent is

embedded in a composite matrix containing a catalyst capable of polymerizing the healing
agent. Source: White et al. 2001 [32]. Reprinted with permission of Nature Publishing Group.
(b) Schematic illustration of a cut in the epidermis layer of the skin and the capillary network in
the dermis layer. (c) Schematic view of a vascular self-healing system, consisting of an
interpenetrating microvascular network that supplies two fluids (red and blue) to a crack
plane, where mixing occurs (purple). Source: Hansenet al. 2009 [49]. Reprinted with permission
of John Wiley and Sons.
continuously delivered to cracks via the microvascular networks and heal the
damage (Figure 5.1c). The existence of such microvascular networks guarantees
the large-volume and repeatable self-healing of mechanical damage on the
same damage region. Meanwhile, such extrinsic self-healing materials mostly
exhibit autonomic self-healing without any trigger, which the damage itself can
stimulate the process of self-healing.
Even though large-volume self-healing can be realized, some disadvantages also
exist, including relatively complicated design and fabrication process, as well as
slow and limited-time healing since the amount of healing agents is depleted in
the healed region. Moreover, the damage regions that are not lying in the path of
microcapsules would not be healed.
5.3.2 Intrinsic Self-Healing Materials

In contrast, intrinsic self-healing materials do not need an additional healing
agent, and the molecules that constitute the matrix can act as the healing agent
by themselves [1, 10].
The healing process involves polymer chain internal diffusion or/and external
migration to form reversible covalent bonds and noncovalent bonds, depending
on system design [50–53].
5.3 Extrinsic and Intrinsic Self-Healing Materials 161
Bond reformation
Network repair
Physical damage
Segmental mobility and

conformational changes bring
reactive chain ends to contact
Diffusion of low molecular
weight segments
Physical damage:
Chain cleavage
Chain slippage
Result: Reactive chain ends
Undamaged network
Evolution of damage and repair
Figure 5.2 Schematic illustration of the evolution of an ideal damage-repair process in

polymeric materials. Source: Yang and Urban 2013 [54]. Reprinted with permission of Royal
Society of Chemistry.
Upon structural damage, cleavage of polymer chains leads to the release of

reactive groups (either pendent groups or cleaved chain ends), such as free rad-
icals and/or —C—C—, —COOH, —NH2 , —OH, —Si—O, SH/S—S, or —C—O,
which facilitate re-bonding to realize self-healing [54]. As depicted in Figure 5.2,
mechanical damage could cause polymer network cleavage and/or slippage. Sub-
sequently, the resultant migration and/or diffusion of polymer chains leads their
reactive groups in contact with each other to heal the wound by bond refor-
mation and physical network repair. Additionally, for special wetting surfaces,
self-healing stems from the free-energy-driven self-migration of hydrophobic or
hydrophilic polymer chains to heal the damaged surface chemical component.
Generally, most covalent bonds are irreversible, and hence conventional
covalent polymers are permanently damaged by the formation and propaga-
tion of cracks. However, reversible covalent linkages have been exploited to
realize self-healing by reforming new bonds toward the damaged site [55].
Reversible covalent bonds are based on reversible chemical reaction, such as
Diels–Alder (DA) reaction, disulfide bonds, reversible radical reactions, and
photocycloaddition [10, 56–61]. Due to their high bonding strength, reversible
covalent polymers mainly are applicable for the majority of polymeric structural
engineering materials [62].
Additionally, reversible noncovalent bonds in polymers can also be exploited
for self-healing performance [54], consisting of hydrogen bond [63, 64],
metal–ligand bonding [65–67], ionic interaction [68], host–guest interaction
[69], π–π interaction [70], and so on. The majority of reversible covalent
cross-linking requires relatively complex treatment, like thermal or light treat-
ment, to trigger the reaction. In contrast to the covalent interaction, materials
associated by noncovalent bonds can achieve the self-healing process under more
mild conditions with a higher spatial density of bonding [1, 69, 71]. Furthermore,
since noncovalent bond interactions have relatively lower strength as compared
with the covalent bonds, they are highly reversible and easily accessible to be
incorporated into polymer structures to realize self-healing. Nevertheless, the
ultimate and ideal goal is to develop materials with the capability of autonomous
self-healing.
As a consequence, intrinsic self-healing mode further avoids some issues
of integration and healing-agent compatibility that arise in vascular and
capsule-based self-healing materials. Meanwhile, intrinsic self-healing materials
can achieve multi-time reversible healing through inherent reversibility of
molecular interactions of the matrix polymers. Moreover, intrinsic self-healing
systems are able to heal tiny damages even at the molecular scale. In contrast,
capsule- or vascular-based healing systems are only applicable to heal large
damage volumes.
Hence, such intrinsic self-healing materials can achieve high flexibility, fast
healing, biocompatibility, and incorporation of multifunctions. Due to these
advantages, more attention has been held on the intrinsic self-healing materials
with specific functions suitable for environmental applications than the extrinsic
self-healing materials.
5.4 Self-Healing Materials in Environmental

Applications
Overall, triggered by damage or external stimuli, healing agent from self-healing
systems can be initiated and move toward damage sites via extrinsic or intrinsic
self-healing approach to achieve self-healing process (Figure 5.3). The damages
of materials generally include physical crack and surface function loss. The latter
one may be owing to the removal of surface chemically functional components
or due to surface contamination [30, 72, 73].
Accordingly, the following discussions are organized into three parts (i)
self-healing of physical cracks, (ii) self-restoring of surface chemical compo-
nents, and (iii) self-cleaning of contaminated surfaces. The following sections
present and discuss the examples of self-healing materials, which have been
preliminarily applied into the environmental field in the above categories. As the
concept of self-healing has slowly but steadily been appreciated by and applied
to environmental fields in the past decade, some exploratory works on endowing
conventional environmental processes with self-healing materials have been
Extrinsic Damage
Physical
self-healing itselt
Self- crack
materials External Damage
healing Triggers Surface
Intrinsic stimuli sites
agents self-healing (heat, light, function
...) loss
materials
Figure 5.3 Classification of self-healing materials.

5.4 Self-Healing Materials in Environmental Applications 163
conducted, including, but not limited to, water filtration [74–76], oil/water
separation [77], pollutant absorption [78], antifouling surface, etc. [79–81].
5.4.1 Self-Healing of Physical Cracks

During the installation and operation of materials and devices, accidents and
wear and tear often lead to cracked damages, which are detrimental to their
designed performances. Endowing these materials and devices with self-healing
capability would prolong their lifetime and reduce operational cost. The
self-healing of physical crack is a broad topic, and this part of the chapter focuses
only on the recent development of the application of self-healing materials to
environmental processes.
The application of self-healing materials that can heal physical cracks in
environmental processes is relatively new. In 2012, Tyagi et al. reported a porous
membrane by assembling micelles of triblock copolymer poly(styrene-co-
acrylonitrile)-b-poly(ethylene oxide)-b-poly(styrene-co-acrylonitrile) (PSAN-b-
PEO-b-PSAN) for water filtration (Figure 5.4) [74]. The evaporation of the
copolymer solvent results in the formation of a porous film through the dynamic
self-assembly of micelles with the diameter of 50 nm. The membrane material
was not cross-linked and therefore could self-heal its macroscopic structural
defects under an applied pressure of 0.8 bar by the rearrangement of micelles
and the reformation of block copolymer bridges on the damage site.
Furthermore, in 2016, Kim et al. fabricated a self-healing filtration membrane
by embedding the extrinsic microcapsules composed of PU shell and IPDI core
into PES membrane [75]. Once damaged, the healing agent of isocyanate was
released from the broken microcapsules and diffused toward the crack sites and
then reacted with the surrounding water to form PU plug to cover the dam-
age sites (Figure 5.5a). Once healed, the water flux and particle rejection perfor-
mances of the membrane were recovered to 103% and 90% of the original ones,
respectively.
Nevertheless, the microcapsule-type extrinsic self-healing agent results in a
limited number of healing cycles at a given region. Kim and coworkers further
developed a water filtration PES membrane with membrane pores filled with
poly(2-acrylamido-2-methyl-1-propane sulfonic acid) (PAMPS) hydrogel [76].
The self-healing capability of the membrane was majorly attributed to the
swelling effect of the pore-filling hydrogel at the damage site and the strong
hydrogen bonding and molecular interdiffusion of the hydrogel polymer chains
(Figure 5.5b). As a consequence, the particle rejection efficiency of the healed
membrane restored to 99%, while the efficiency of the damaged membrane
was as low as 30%. In 2017, the same group further developed an improved
in situ healing method by using branched polyethylenimine-functionalized
silica microparticles [82]. The in situ healing recovered the membrane’s particle
rejection to 99.1% of the original one without any flux decline.
In 2013, Lu and coworkers fabricated a self-healing and pollutant-adsorbing
hydrogel by using polydopamine (PDA)-modified clay as the main building
block and Fe3+ ions as the physical cross-linkers (Figure 5.6a) [78]. Upon the
removal of applied large stress, this hydrogel could be self-healed via reformation
COOH
O
O O
N O O
y x m O n x y mO N
EtO P CN
CN O P OEt
OEt
COOH OEt
(a)
Solvent concentration
(b) Nanoporosity
S–4800 ×50.0k
600 nm
(c)
Figure 5.4 (a) Chemical structure of the triblock copolymer. (b) Sketch of the membrane
formation: during the course of the solvent evaporation, the increase of the block copolymer
concentration triggers their self-assembly into micelles, which assemble in three dimensions
forming a dynamic interactive membrane film. (c) SEM image of the film. Source: Tyagi et al.
2012 [74]. Reprinted with permission of John Wiley and Sons.
of damaged catechol–Fe3+ complexes. Moreover, working as an adsorbent, it

effectively removed an organic pollutant Rhodamine 6G (Rh6G) from water
with an adsorption capacity of 150 mg g−1 owing to the hydrogen-bonding and
π–π stacking interactions between the aromatic moieties of PDA and Rh6G.
As demonstrated in Figure 5.6b, after dye-containing water was slowly poured
through a hydrogel-filled syringe, the Rh6G was trapped in the hydrogel, while
Polyurethane Healed site

microcapsules
Membrane
Broken
microcapsules
(a) Nonwoven fabric
Pristine membrane Damaged membrane Healed membrane
Hydrogel
expansion
Molecular
interdiffusion
O O
S OH
N
O
Pore-filling Support Hydrogen H H
n
O
hydrogel substrate bonding N
HO S
n
O O
(b)
Figure 5.5 (a) Schematic illustration of the self-healing process of microcapsule-embedded

membranes. Source: Kim et al. 2016 [75]. Reprinted with permission of American Chemical
Society. (b) Schematic illustration of self-healing pore-filled membranes with the pore-filling
hydrogel anchored on PES membrane that acted as the active layer by allowing water to pass
through and repelling unwanted particles (red spheres). Source: Getachew et al. 2017 [76].
Reprinted with permission of American Chemical Society.
D-clay hydrogel Fe3+ as cross-linker for D-clay
Water
with
Rh6G
Fe3+
Clay Rh6G
removed
A thin layer of
PDOPA coating
(a) (b)
Figure 5.6 (a) Schematic illustration of the formation mechanism for the hydrogels.
(b) Photograph showing the removal of Rh6G by the hydrogel. Source: Huang et al. 2013 [78].
the clear water could pass through the hydrogel and could be observed at the
end of the syringe, indicating the complete removal of the Rh6G dye.
Except that, in 2014, Yan et al. described a self-healing supramolecular gel that
was prepared from tetrazolyl derivatives and alkylamine via hydrogen-bonding
self-assembly [83]. This gel could selectively congeal crude oil from an oil/water
mixture and displayed remarkable self-healing properties. It is noted that hydro-
gels with self-healing properties provide a great promise in biological tissues and
environmental applications owing to their hydrated nature and biocompatibility.
In 2015, Sun and coworkers fabricated self-healing and antifouling films via
layer-by-layer (LbL) assembly of PEGylated branched poly(ethylenimine) (bPEI)
and hyaluronic acid (HA). The damaged structure and antifouling function of
the films could be healed rapidly in water due to the high mobility of polyelec-
trolytes and the resultantly rapid reformation of reversible electrostatic and
hydrogen-bonding interactions [84].
Similarly, in the same year, Zeng and coworkers reported a mussel-inspired
injectable hydrogel with self-healing and anti-biofouling capabilities, which
was based on self-assembly of triblock copolymer consisting of PNIPAM and
poly(ethylene oxide) (PEO) [85]. The obtained hydrogel remained its self-healing
ability with experiencing repeated structural damage through catechol-mediated
hydrogen-bonding interactions and aromatic interactions (Figure 5.7) and also
Hydrogen bonding
H
OH H O
O
O H HO
H H
O
OH
O HO
H
OH
HO
O
H
HO
H O
H
Aromatic interaction
HO OH OH
HO
HO OH
HO
HO
PEO
Cross-link with catechol groups (red tetragon)

trapped into the PNIPAM block (blue dot)
Figure 5.7 Schematic illustration of the chemical structure of the triblock copolymeric
hydrogel. Source: Li et al. 2015 [85]. Reprinted with permission of John Wiley and Sons.
effectively prevented nonspecific cell attachment owing to the presence of PEO

with strong antifouling property.
The membrane technology in CO2 separation and capture is significantly
beneficial to address the risk in the greenhouse gas emission, and as a novel
research direction, this technology has more advantages than traditional method
owing to its less energy consumption and satisfying ecofriendly needs. However,
in practical use, even subtle crack in the membrane would lead to entirely
losing the original functions. Hence in 2018, Cao et al. reported a self-healable
polymeric elastomer with recoverable gas-separation performance, which
was synthesized by reacting urea with amine-terminated PDMS elastomers
[86]. The obtained elastomers exhibited an extremely high elongation at break
(984–5600%) with adjustable mechanical strength, elasticity, and extensibility.
After mechanical damage, mechanical strength and gas-separation performance
Applied
scratch After
healing
(a)
5 × 103
Original
Permeability (barrier)
4 × 103
After healing
3
3 × 10
2 × 103
1 × 103
15
Selectivity/α (CO2/N2)
10
0
(b) U-PDMS0.9K-E U-PDMS3.0K-E U-PDMS5.0K-E U-PDMS30K-E
Figure 5.8 (a) Images showing the gas-separation membranes with applied scratch and after
healing at 40 ∘ C for 30 minutes. (b) Comparative CO2 permeability (up) and CO2 /N2 selectivity
(bottom) of original polymeric membranes (blue) and polymeric membranes after cut and
healing (orange). Source: Caoet al. 2018 [86]. Reprinted with permission from of John Wiley
and Sons.
with CO2 permeability and CO2 /N2 selectivity can be healed in 120 minutes at
ambient temperature or in 30 minutes at 40 ∘ C (Figure 5.8).
In addition, the liquid-repellent surfaces have been widely investigated in fuel
transport, antifouling, and other potential environmental applications. Mean-
while, the introduction of the self-healing capability can enhance the service
life term and stability upon physical damage [87]. In 2011, Wong et al. reported
a self-healing slippery liquid-infused porous surface (SLIPS) with exceptional
liquid and ice repellency, pressure stability, and enhanced optical transparency
[88]. This surface was capable to repel various simple and complex liquids such
as water, hydrocarbons, crude oil, and blood, with low contact angle hysteresis
(CAH) (<2.5∘ ), and could resist ice adhesion and remain its functions at high
pressures (up to about 680 atm). Serving as an intelligent coating with self-healing
performance, it rapidly and repeatedly restored the liquid-repellent function
(within 0.1–1 second) upon large-area physical damage by recurring abrasion or
impact, since the fluidic nature of the lubricating layer forced the liquid to flow
toward the damaged area by surface-energy-driven capillary action (Figure 5.9).
Following this concept, in 2013, Vogel et al. employed colloidal templating to
design transparent, slippery liquid-infused nanoporous surface structures with
self-healing capability [89]. (1H,1H,2H,2H-Tridecafluorooctyl)-trichlorosilane
was locked into the porous network and formed a stable liquid film. The
obtained film exhibited efficient liquid repellency, prevention of adsorption of
liquid-borne contaminants, reduction of ice adhesion strength, and the unique
self-healing properties arising from the liquid nature of the lubricant.
In 2018, Heng and coworkers further developed an anisotropic slippery surface
using directional, porous, and conductive polymer (PCDTPT) films and silicone
oils with different viscosities, which combined with self-healing property and
electrically driven smart control of droplet motion [90]. As a result, the critical
self-healing thickness increased with increasing silicone oil viscosity. On the
other hand, the responsive voltage for controlling the droplet sliding motion
reduced with decreasing the viscosity of silicone oil.
Earthworm could pass through sticky soil without inducing stains due to a
self-recovery thick lubricating layer on their texture skins. Recently, inspired
by earthworm, Cui and coworkers created artificially intelligent coatings with
self-replenishing lubrication for adaptive friction reduction, wear resistance,
and antifouling property in a solid environment [91]. As shown in Figure 5.10a,
lubricants were embedded as discrete droplets into a supramolecular polymer
matrix made from the copolymer of urea and PDMS. Meanwhile, the poly-
meric surface was prepared through the solution casting method under humid
conditions where solvent (THF) evaporation would induce water condensation
on the forming polymer surface and thus rough structure formed directly
(Figure 5.10b). The obtained coatings exhibited self-regulated liquid release
since the lubricant stored in the droplets could be site specifically and quickly
released under external mechanical stimulus, thus to restore oil layer and heal
the slippery functional surface (Figure 5.10c).
Ice accretion poses a severe risk for human safety, and traditional methods
of ice removal using antifreeze fluids or heating, caused high energy con-
sumption and unavoidable environmental problems. SLIPS possess icephobic
Slips
t = 0 ms 1 cm Tilting = 5° Tilting = 5° Tilting = 5°
Damage
Physical Crude
oil
damage
5 mm
t=0s t=1s t=2s
Teflon AF treated flat surface
t = 150 ms Tilting = 5° Tilting = 10° Tilting > 10°
Self-healed 1 cm
Crude oil
Physical
damage Pinned
droplet Pinned
droplet
t=0s t=2s t = 17 s
(a) (b)
Figure 5.9 Self-healing and optical transparency of SLIPS. (a) Time-lapse images showing the self-healing capability of an SLIPS upon physical damage, 50 mm
wide on a timescale of the order of 100 ms. (b) Time-lapse images showing the restoration of liquid repellency of an SLIPS after physical damage, as compared
to a typical hydrophobic flat surface (coated with DuPont Teflon AF amorphous fluoropolymers) on which oil remains pinned at the damage site. Source:
Wong et al. 2011 [88]. Reprinted with permission of Springer Nature.
(i) Solvent evaporation in moist air (ii) Locking of liquid layer
uPDMS, silicone oil, THF Breath figure

phase separation
gelation
uPDMS: Liquid supplying regime
(iv) Rebuilding of liquid layer (iii) Consumption of surface liquid
Mechano-stimulus
Silicone oil Gel matrix

(a)
2h 5h 12 h
50 μm 50 μm 50 μm
(b)
Washed film
Pressed region
200 μm 200 μm
(c)
Figure 5.10 The fabrication and the liquid-release process of gel films. (a) Schematic
illustration of the synthetic strategy and stimuli-responsive release of the polymer coating.
(b) Top-view image of polymer coating formed at different times. (c) The oil release behavior of
a freshly water-washed sample under a local pressing. The thickness of the films in (b) and (c) is
about 400 μm. Source: Zhao et al. 2018 [91]. Reprinted with permission of John Wiley and Sons.
surface with low ice adhesion strengths below 15, 1.7, and 0.4 kPa in different
studies [92–94]. Short life spans of state-of-the-art icephobic surfaces still
need to address. In 2018, Zhang’s group integrated an interpenetrating poly-
mer network (IPN) into an autonomous self-healing elastomer, consisting of
Fe-pyridinedicarboxamide-containing PDMS (Fe-Py-PDMS) and commercial
PDMS (Sylgard 184) [95]. Fe-Py-PDMS, as a self-healing elastomer with low
modulus and surface energy, is cross-linked via metal–ligand coordination
bonds, while Sylgard 184 is cross-linked via covalent bonds (Figure 5.11). The
obtained material realized an ultralow ice adhesion strength of 6.0 ± 0.9 kPa and
remained at a low value of ∼12.2 kPa after 50 icing/deicing cycles. Meanwhile,
such material can be self-healed upon mechanical damage in 24–48 hours.
CH3 CH3
Si O x Si O
y
CH3 CH2
CH2 CH3
O Si y O Si x
CH3 CH3
Sylgard 184
O
CH3 CH3 CH3 N m
NH Si O Si O Si N O CH3 CH3 CH3
n Fe
CH3 CH3 CH3 O N Si O Si nO Si NH
m
N CH3 CH3 CH3
O
Fe-Py-PDMS
Figure 5.11 Scheme of the self-healing IPN elastomer consisting of Fe-Py-PDMS and Sylgard
184. Source: Zhuo et al. 2018 [95]. Reprinted with permission of American Chemical Society.
5.4.2 Self-Restoring of Surface Functional Components

The surface function, especially surface wettability, is usually achieved by
depositing an ultrathin functional layer (e.g. a single molecular layer) on a
substrate material, which makes the surface function being easily degraded
even without any appreciable structural cracks. Accordingly, developing durable
wetting surface materials with self-healing capability has become one of the most
intriguing topics in the area of surface science, especially involving self-healing
liquid-repellent surfaces and highly hydrophilic antifouling surfaces.
5.4.2.1 Chemical Mechanism

Particularly, the self-healing of surface wettability (e.g. hydrophobicity,
hydrophilicity) is largely based on the surface-free-energy-driven migration of
hydrophobic or hydrophilic polymer chains. In practice, surface hydrophobic
molecules can be gradually decomposed or removed by mechanical damage
or upon exposure to light irradiation and highly oxidative chemicals. With the
hydrophobic molecules gone from the surface, the surface energy would rise
in the air due to the exposed hydrophilic groups. Then the low-surface-energy
molecules underneath/near the damaged sites would migrate onto the outer
surface to reduce the surface energy and restore the original hydrophobicity
[96]. Alternatively, this process can also be explained by the fact that the air
is a very hydrophobic medium and the low-surface-energy molecules like to
make contact with the air according to the principle of “like dissolves like.”
Additionally, except the automatic process of self-healing, such motion and
migration of healing agent can be initiated or accelerated by external stimuli,

such as heating [97–99], moisture [100], solar irradiation [101–103], organic
solvent [104], etc.
Similarly, for the hydrophilic surfaces, after the hydrophilic polymer chains
were degraded or detached from the surfaces, the polymer chains stored inside
the matrix would spontaneously migrate to the damaged surface to form a new
hydrophilic polymer layer, which was driven by an emerging gradient in a chem-
ical potential or free energy [79]. As can be derived, for the above self-healing
mechanisms to work, a matrix to store the self-healing components is needed.
5.4.2.2 Hydrophobic Self-Healing

As a proof to this surface wettability self-healing concept, in 2010, Sun and
coworkers reported a self-healing superhydrophobic coating, which was fabri-
cated by chemical vapor deposition (CVD) of fluoroalkylsilane on the porous
LbL-assembled polyelectrolyte film [96]. As Figure 5.12 shows, the surface
superhydrophobicity, once lost, could be self-restored at room temperature by
means of self-migration of fluoroalkyl chains from the underneath polyelec-
trolyte film to the outer surface to minimize the interfacial free energy. The
moisture could accelerate the rate in self-healing since after decomposition of the
superhydrophobic layer, the surface became superhydrophilic and can absorb
water in a humid environment, which further softens the coating matrix and
1 2 3
Decompose Self-healing
H2
C CH
3
F F F F F O H2
F H2 Fluoroalkyl chain
Si O C
C C C C CH3
F C C C C in reacted POTS
H2 O CH
F F F F F F C 3
(a) H2
POTS
C O O
n
(b) SO3H
Figure 5.12 (a) Working principle of self-healing superhydrophobic coatings. (1) The porous
polymer coating with micro- and nanoscaled hierarchical structures can preserve an
abundance of healing agent units of reacted fluoroalkylsilane. (2) The top fluoroalkylsilane
layer is decomposed, and thus the coating loses its superhydrophobicity. (3) The healing
agents can migrate to the coating surface and recover superhydrophobicity. (b) Chemical
structure of sulfonated poly(ether ether ketone) (SPEEK). Source: Li et al. 2010 [96]. Reprinted
with permission of John Wiley and Sons.
drives the migration of fluoroalkyl chains. Also, such restoration process could
be repeated many times without decreasing the superhydrophobic property.
Even since, the self-healing superhydrophobic coatings and textiles have been
widely prepared from a variety of polymers, such as 1H,1H,2H,2H-perfluoro-
octyltriethoxysilane (POTS) [105], fluorinated-decyl polyhedral oligomeric
silsesquioxane (FD–POSS) [106–108], fluorinated alkyl silane (FAS) [102, 106,
109], perfluorooctanesulfonic acid (PFOS) lithium salt [105], perfluorooctyl acid
[110], poly(2,2,3,3,4,4,4-heptafluorobutylmethylsiloxane) (PMSF) [101], PDMS
[104], and octadecylamine (ODA) [100].
In 2015, Wang and coworkers further applied this superhydrophobicity
self-healing mechanism to a photothermal conversion membrane, which was
the first report on using polymeric photothermal materials, for the purpose of
solar-driven water evaporation and seawater desalination (Figure 5.13a). The
membrane was fabricated by deposition of light-to-heat conversion material
of polypyrrole onto a porous stainless steel mesh, followed by hydrophobic
fluoroalkylsilane modification [111]. As-prepared membrane can self-float at
the water/air interfaces to realize automated and uninterrupted interfacial solar
heating. By locally heating the interfacial water under light irradiation, the
PPy-based hydrophobic membrane rises the rate of water evaporation. More
importantly, it was revealed in this study that the migration and enrichment of
fluoroalkyl chains to the outer surface of the coating could be accelerated by solar
light irradiation and multiple cycles of self-healing were achieved (Figure 5.13b).
In 2016, Fang et al. demonstrated a self-healing electrospun N-perfluorooctyl-
substituted PU fibrous membrane for oil/water separation [77]. The membrane,
with O2 plasma treatment, lost its superhydrophobicity but could recover its
superhydrophobicity back with assistance by gentle heat treatment for more than
70 cycles. The oil/water separation efficiency maintained at above 98% after 20
cycles of wettability loss-and-restoration cycles since the fluorine-containing PU
could self-migrate to the outer surface of the fibers to restore the superhydropho-
bicity of the membrane. Accordingly, upon plasma-and-heating treatment, the
Point-of-use solar distillation device

160
Contact angle (°)
Solar-powered fan
120
Condensing
Plasma
treatment
irradiation
chamber 80
Light
Evaporation
chamber 40
0
PPy-coated mesh membrane

0 1 2 3 4 5
Healing cycles
(a) (b)
Figure 5.13 (a) Schematic configuration of the point-of-use device for direct and all-in-one
solar distillation. (b) Reversible water contact angle changes on the plasma-treated and
light-irradiated PPy-coated mesh. The insets in (b) were the shapes of the water droplets on
the surfaces after plasma treatment and light irradiation. Source: Zhang et al. 2015 [111].
Reprinted with permission of John Wiley and Sons.
6000 n-Hexane 100

Ether
Separation efficiency (%)

Permeate flux (l m–2 h–1) Petroleum ether
5000 Toluene 98 n-Hexane
Bromoethane
Petroleum ether
4000
96 Bromoethane
3000 Ether
94 Toluene
2000
1000 92
0 90
0 5 10 15 20 0 5 10 15 20
(a) Self-healing cycles (b) Self-healing cycles
Figure 5.14 Permeate flux (a) and separation efficiency (b) of the electrospun N-
perfluorooctyl-substituted PU fibrous membrane after 20 self-healing cycles. Source: Fang
et al. 2016 [77]. Reprinted with permission of John Wiley and Sons.
oil permeation flux experienced only a small decline for a variety of oils (7.8% for
n-hexane, 8.5% for petroleum ether, 8.7% for bromoethane, 8.1% for ether, and
8.2% for toluene) (Figure 5.14a,b).
In the same year, Liu and coworkers fabricated a self-healing anti-smudge
coating by modifying LbL-assembled poly(diallyldimethylammonium) (PDDA)
and poly(styrenesulfonate) (PSS) film with perfluorooctanoate (PFO) [81]. The
film can be deposited onto various commonly available substrates (e.g. Si, glass,
plastic, steel, and wood). The modified film on these substrates all showed
sliding angle <12∘ for a variety of low surface tension liquids of 10 μl and easily
self-restored its oil repellency upon lost due to the replenishing surface.
In 2017, in Guo’s group, superhydrophobic fabrics were prepared through an
in situ growth method for depositing MnO2 nanoparticles on cotton fabric sur-
face to construct a hierarchical structure and subsequent stearic acid modifica-
tion for lowing the surface energy [112]. The obtained fabrics can automatically
recover their superhydrophobicity by a short-time heat treatment, without obvi-
ous reduction on the water CA after 8 cycles of the repetitive etching–heating
cycles. Meanwhile, the self-healing superhydrophobic fabric exhibited excellent
mechanical stability, wear resistance, and high efficiency of oil/water separation.
5.4.2.3 Hydrophilic Self-Healing

Bio-inspired by fish scales, artificial underwater surface materials with
hydrophilicity enables to repel oils or organic liquids only when submerged in
water. This kind of functional surface is commonly utilized as antifouling mate-
rial operating in seawater or resisting the undesirable adhesion of protein, cells,
and microorganisms [113–116]. Undoubtedly, physical rubbing or damage in an
underwater environment could cause the loss of superoleophobic or antifouling
properties of the functional surface, accordingly recalling the introduction of
self-healing design for long-lasting use and operation.
In 2013, Minko and his coworkers grafted PEO both on the surface and inside
of P2VP polymer 3D network [79]. When the surface was damaged underwater,
the grafted PEO polymers residing in a polymer network underwent a spon-
taneous rearrangement and migration to replenish the lost PEO chains at the
Surface grafting
PEO brush
Fouling
Network
Degradation
Substrate
(a)
Self–healing
antifouling surface
PEO brush 3D grafting
Degradation
Network
with the grafted PEO
Replacement
(b) of the detached chains
Figure 5.15 Schematic illustration of the PEO-grafted P2VP network films. (a) The grafting of
PEO to the surface of a P2VP film and (b) 3D polymer grafting on the surface and inside of a
P2VP film. The self-healing aspect of the antifouling property is due to the rearrangement of
internally grafted polymers to the interface (marked as dark blue chains). Source: Kuroki et al.
water–network interface (Figure 5.15). As a result, the antifouling performance of

the material showed a fourfold increase as compared with the traditional antifoul-
ing materials in physiological conditions (pH 7.4 and 37 ∘ C). Furthermore, owing
to the existence of the P2VP block, PEO-grafted P2VP films also demonstrated
the high stability of pH-responsive performance during the healing process.
Based on the same concept, in 2015, Wu and coworkers fabricated a similar
material by grafting self-assembled hydrophilic copolymeric chains on the
hierarchical microgel spheres. The prepared material achieved the capability of
self-restoring antifouling properties once its surface is mechanically damaged
(Figure 5.16a) [80]. Due to the swelling of the microgel spheres and movement of
Water
: MHMS : Thermoset acrylate resins and t-HDI Oil
Underwater
Abrading or superoleophobic
crushing Self-healing Protein
Water
Anti-biofouling
(a)
Surface
Press Retract
160
OCA(°)
(c) Water
155
Surface
150 Press Retract
Oil repellent
Oil adhesive
0 1 2 3 4 5 6
(b) (d) Water
Crushing-repairing cycles
Figure 5.16 (a) Schematic illustration of the structure and self-healing process of underwater
superoleophobic and anti-biofouling coating. (b) Changes of OCAs of hexadecane on the
MHMS-based coating as a function of the cycle number of the crushing and self-repairing. The
images show that the oil droplet of hexadecane is adhesive on the pressed surface (c) or
nonadhesive on the surface of the immersed coating at 20 ∘ C for 25 minutes (d). Source: Chen
et al. 2016 [80]. Reprinted with permission of American Chemical Society.
hydrophilic polymeric chains in the coating, this crushed surface can recover its
original underwater superoleophobicity (Figure 5.16b) and acquire oil-repellent
property again after cycles of press and immersion in water at 20 ∘ C for
25 minutes (Figure 5.16c,d).
5.4.3 Self-Cleaning of Contaminated Surfaces

Self-cleaning is a desired performance for human beings and applicable in a wide
domain of promising practical applications, such as industry, agriculture, and
the military [117, 118]. However, the surfaces of environmental materials dur-
ing their applications inevitably suffer from the contaminant, such as attach-
ment and absorption of dirt, bacteria, oil, and protein, resulting in weakened and
impaired surface structures and performances [119]. Therefore, materials with
self-cleaning surfaces are highly desirable in many environmental processes and
are necessary before ideally antifouling surfaces, if any, can be developed.
With the great progress on the different synthesis strategies and designs of
self-cleaning surfaces, recently, a wide range of self-cleaning surfaces have also
been commercialized [120, 121]. According to the mechanism of self-cleaning,
the majority of self-cleaning surfaces can be placed into three categories: super-
hydrophobicity, superhydrophilicity, and photocatalysis.
5.4.3.1 Superhydrophobicity-Induced Self-Cleaning

The self-cleaning effect of lotus leaves was observed 2000 years ago in Asia
as a miracle. However, the actual mechanism behind the mysterious miracle
was not scientifically revealed until the 1960s when the modern scanning
electron microscope (SEM) was developed [122, 123]. Lotus leaf surfaces
possess superhydrophobic and low-adhesion characteristics with water CA of
160∘ and SA of 2∘ , due to the combination of micro/nanoscaled hierarchical
structures and hydrophobic epicuticular waxes. Inspired by lotus leaves, a
multitude of self-cleaning materials with superhydrophobicity and low-adhesion
characteristics have been fabricated, which have very high water contact angles
(CAs) (>150∘ ), small water sliding angles, and small CAH (<10∘ ) in air (Cassie
state) [122, 124, 125]. Water on such self-cleaning superhydrophobic surface
tends to form spherical droplets, which can easily roll off the surface and
meanwhile carry dust and dirt with them to achieve the self-cleaning property
[122, 125–128]. In recent years, the self-cleaning superhydrophobic materials
have been widely applied in the fields of antifogging [129, 130], anti-icing [131],
corrosion resistance [132–134], solar water evaporation [135], light energy
harvesting by solar cell [136, 137], water drop energy harvesting [137, 138], etc.
For example, in 2015, Jiang and coworkers designed a carbon-black-based
superhydrophobic gauze that floats on the water surface and locally heats at
the air/water interface under solar irradiation, resulting in the enhancement
of evaporation rate [135]. Furthermore, the superhydrophobic black gauze was
endowed with self-cleaning ability, arising from its high water repellency and low
water adhesive force. As shown in Figure 5.17, a moving water droplet effectively
picked up the surface contamination of the NaCl crystals without any residue in
the superhydrophobic surface, revealing a lotus-leaf-like self-cleaning ability.
In the same year, Choi and coworkers fabricated a transparent hybrid cell
with the self-cleaning property that was able to complementarily harvest
raindrop and solar energy with immunity to dust contamination [137]. Such
hybrid cell consists of transparent triboelectric nanogenerator (TENG) and
conventional solar cell, and the transparent TENG was fabricated with PDMS
and indium tin oxide/polyethylene naphthalate (ITO/PEN) substrate. Due to
Contact and move
NaCl crystal
(a) (b) (c)
“Pick up” NaCl Self-cleaning
(d) (e) (f)
Figure 5.17 Demonstration of the self-cleaning ability of the superhydrophobic black gauze.
A moving droplet can effectively remove the surface contamination of NaCl crystals. Source:
Liu et al. 2015 [135]. Reprinted with permission of American Chemical Society.
the superhydrophobicity of the PDMS with the microbowl array, the solar cell
efficiency of the hybrid cell could recover to 84% after a cleaning process.
5.4.3.2 Superhydrophilicity-Induced Self-Cleaning

∘
In case of superhydrophilic surfaces, the surfaces have water CA as small as 0
and allow water to spread out quickly to form a thin water film between fouling
debris and the underneath surface, which leads to separation of the debris from
the surface [125, 139–141].
On the other hand, hydrophilic polymers have been widely employed to
make self-cleaning and antifouling coatings [142]. Commonly, these antifoul-
ing surfaces have been reported through surface modification of hydrophilic
polymers onto substrates, especially involving PEO, PNIPAM, zwitterionic
polyelectrolytes, and copolymers with hydrophilic domains [139–141, 143–147].
PEO is commonly used in antifouling application since PEO molecule can
tightly bind with water by hydrogen-bonding interaction and form a powerful
barrier to resist fouling adsorption. Furthermore, PNIPAM-based materials
can perfectly release fouling only by low-temperature water rinsing due to the
hydrophilicity transition below LCST. In terms of zwitterionic polyelectrolytes,
zwitterions integrating both positively and negatively charged units in one group
can superiorly bind water molecules via electrostatically induced hydration. As a
result, a tightly bound water layer could be produced at the surfaces contacting
with water and form a barrier for self-cleaning and biofouling [140, 148–150].
For example, in 2015, Liu and coworkers grafted poly(2-methacryloyloxylethyl
phosphorylcholine) (PMPC), a typical zwitterionic polyelectrolyte, onto steel
meshes [141]. The PMPC modified meshes not only exhibited complete oil
repellency in a water-wetted state but also realized effective cleaning of oil
contamination on dry surfaces with simply water rinsing due to the high water
affinity of zwitterionic phosphorylcholine groups. As shown in Figure 5.18a, the
Nile red-labeled oil that fouled on the dry PMPC mesh underwent complete
dewetting and detachment in only 1.12 seconds after immersion into water,
which enabled a thorough cleaning of the oil-fouled surface by water washing
(Figure 5.18b).
In 2016, Jin and coworkers reported a sodium polyacrylate-grafted
poly(vinylidene fluoride) (PAAS-g-PVDF) hydrogel membrane via an
alkaline-induced phase inversion process, which possessed underwater
anti-crude-oil-adhesion property [151]. PAAS-g-PVDF exhibited underwater
ultralow-oil-adhesion and self-cleaning properties to crude oils with underwater
oil CAs all above 165∘ and nearly zero underwater oil adhesion force due to
the strong hydration capability of PAAS (Figure 5.19). A PAAS-g-PVDF-coated
copper mesh can effectively separate crude oil/water mixtures with high flux
up to 50 000 l m−2 h−1 and high separation efficiency of 97.1% and is able to be
recycled for long-term use.
Similarly, Zhang and coworkers reported a hydrogel-embedded tight ultrafil-
tration membrane consisting of sodium polyacrylate-modified polyacrylonitrile
(PAAS-m-PAN) via alkaline-assisted phase inversion process [152]. Driven by
an externally applied pressure of only 1 bar, this membrane can effectively sep-
arate dyes from both monovalent and divalent salts solutions with more than
140 l m−2 h−1 bar−1 water permeance and up to 94% dye rejection. Meanwhile,
t = 1.12 s after immersion

into water
Water
(a)
Under visible light Under UV light
Water washing
Under visible light Under UV light
(b)
Figure 5.18 (a) Photos of stainless steel meshes coated without (left sample) and with (right
sample) PMPC coatings, fouled by 30 μl Nile red-labeled canola oil in air, before (left panel) and
after (right panel) immersion into water. (b) Photos, taken under visible (left panels) and UV
(right panels) light, of the stainless steel meshes coated without (left sample) and with (right
sample) PMPC coatings, fouled by Nile red-labeled canola oil in air, before (upper panels) and
after (lower panels) being washed by water alone. It can be observed that the oil fouled on the
PMPC-coated mesh can be thoroughly cleaned by water washing, as evidenced by the
absence of luminescence of Nile red under UV light. Source: He et al. 2015 [141]. Reprinted
with permission of American Chemical Society.
the PAAS-m-PAN membrane exhibited an unprecedented antifouling property,

without detecting observed dye adhesion on the membrane surfaces.
In 2016, Zhu and coworkers prepared a strong underwater superoleophobic
PNIPAM–clay nanocomposite hydrogel, which was developed as an oil/water
separation filtration membrane [153]. As the hybrid hydrogel was immersed into
crude oil, the adhered oil could be easily cleaned up by water washing, thus indi-
cating ultralow affinity to crude oil.
In 2017, a Janus membrane was designed by integrating an omniphobic sub-
strate and a hydrophilic and underwater superoleophobic surface layer [154]. The
electrospun membrane of cetyltrimethylammonium bromide/poly(vinylidene
fluoride-co-hexafluoropropylene) (CTAB/PVDF-HFP) was decorated with
fluorinated silicon nanoparticles (SiNPs) to serve as the omniphobic substrate
in air. Then the surface layer consisting of SiNPs, chitosan (CTS), and PFO was
applied onto the omniphobic substrate using spray coating (Figure 5.20a). The
Janus membranes maintained stable MD performance with both their fluxes
PAA-g-PVDF Copper mesh Nickel foam Nonwoven PP plastic
5 cm 5 cm 5 cm 5 cm 5 cm
Crude oil Crude oil Crude oil Crude oil Crude oil
(a) CA: ∼165° CA: ∼165° CA: ∼172° CA: ∼167° CA: ∼166°
Nonwoven
(b)
Steel mesh
(c)
Steel mesh
(d)
Latex glove
(e) Coated Uncoated
Figure 5.19 Underwater anti-oil-adhesion and self-cleaning property of PAAS-g-PVDF

coatings. (a) Optical images and underwater crude oil CAs of PAAS-g-PVDF-coated substrates
including copper mesh, nickel foam, nonwoven, and polypropylene (PP) plastic plate. (b–e) A
series of implementing processes to demonstrate the anti-viscous-oil-adhesion and
self-cleaning performance of PAAS-g-PVDF-coated nonwoven (b), stainless steel mesh
(c and d), and latex glove (e). The oil used in (b), (c), and (e) is crude oil. The oil used in (d) is
soybean oil. Optical images in the red frame show the oil fouling of the substrates without
PAAS-g-PVDF coating. Source: Gao et al. 2016 [151]. Reprinted with permission of John Wiley
and Sons.
and salt rejections over 10 hours of operation (Figure 5.20b) and exhibited low
adhesion of oil foulants onto the surface (Figure 5.20c). As-prepared composite
membrane overcame the existing limits in conventional MD membranes,
amphiphilic surfactant-induced wetting and fouling by hydrophobic contami-
nants, and thus enabled an effective desalination of hypersaline wastewater with
complex compositions driven by low-grade thermal energy.
Fibrous network: Second-level reentrant structure

First-level reentrant structure
Electrospinning
Janus(o) top
Florinated SiNPs CTS/PFO-SiNP

CTAB/PVDF-HFP Janus(o) bottom
(positively charged)
composite Janus(o)
(omniphobic)
(a)
Janus(o)
1.2
Normalized flux (J/J0)
100
Before
Salt rejection (%)

1.0
80
Janus(h)
Janus(o)
0.8
0.6
60
0.4 Janus(h) After
Janus(o)
0.2 40
0.0
0 1 2 8 9 10 Non-fouled
(b) Time (h) (c)
Figure 5.20 (a) Fabrication procedure of the Janus membrane. The first step involves
electrospinning a fibrous substrate of CTAB/PVDF-HFP; the second step involves adsorption of
SiNPs followed by surface fluorination; in the last step, a CTS/PFO-SiNP (nanoparticle–polymer
composite) coating was applied onto the omniphobic substrate. (b) Normalized water flux
(blue) and salt rejection (red) for MD wetting experiments. (c) Photographic images of the
membranes before and after the wetting experiments. Source: Huang et al. 2017 [154].
5.4.3.3 Photocatalytic Self-Cleaning

Unlike wetting surfaces that rely solely on water rinsing to clean the surface,
on a photocatalytic self-cleaning surface, the contaminant is washed away due
to the synergistic effect of photocatalysis and photoinduced superhydrophilicity
[118, 128]. Photocatalysis is basically inspired from the photosynthesis process
of the green leaves, which absorb sunlight to drive the chemistry. The artificial
photocatalyst materials commonly stem from semiconductor materials such as
TiO2 , WO3 , ZrO2 , ZnO, CdS, and so forth, which can decompose organic con-
tamination by photocatalyst reaction [118].
TiO2 , as an extensively investigated photocatalyst material, not only possesses
excellent photocatalytic degradation efficiency of organic pollutants in sun-
light but also shows chemical stability under light, low cost, and nontoxicity.
As demonstrated in Figure 5.21, TiO2 can absorb the light energy that is
equal to or higher than its bandgap energy, leading to the generation of the
excited charge carriers, photoelectrons and holes. Therefore, photogenerated
holes can decompose adsorbed organic molecules. Meanwhile, electrons can
integrate with atmospheric oxygen to generate the superoxide radical, which
rapidly attacks surrounding organic molecules. The process of photocatalytic
decomposition exhibits potential self-cleaning ability upon the UV irradiation
[118, 128, 155–157].
hν
hν
– Conduction
band
(a) + Valence
–++ band
– +
+
(a) +– – Photoexcited electron
+ Photoexcited hole
– + +
(b) (d)
A– + D+
– (c)
TiO2
A D
Figure 5.21 Upon irradiation of ultra-bandgap light, the semiconductor undergoes

photoexcitation. The electron and the hole that result can follow one of several pathways:
(a) electron–hole recombination on the surface, (b) electron–hole recombination in the bulk
reaction of the semiconductor, (c) electron acceptor (A) reduced by photogenerated electrons,
and (d) electron donor (D) oxidized by photogenerated holes. Source: Parkin and Palgrave
2005 [118]. Reprinted with permission of Royal Society of Chemistry.
The first photocatalytic self-cleaning surface emerged in 1995 when Paz et al.
fabricated a transparent TiO2 film coating on glass [158]. The photocatalytic
self-cleaning concept later extended into the fields of oil/water separation and
wastewater treatment [159–162]. For example, in 2013, Zhang et al. fabricated
oil/water separation materials with underwater superoleophobicity through
LbL assembly of sodium silicate and TiO2 nanoparticles on a stainless steel
mesh (Figure 5.22a) [163]. Under UV irradiation, the mesh effectively removed
and decomposed fouling oil contaminants, leading to a facile recovery of its
wettability and oil/water separation ability (Figure 5.22b).
Similarly, in 2016, Wang et al. prepared TiO2 -doped PVDF electrospun
nanofibrous membrane for on-demand oil/water separation [160]. The obtained
membrane possesses antifouling and self-cleaning performance, arising from
the photocatalytic property of TiO2 , which has practical significance in saving
solvents and recycling materials.
Since membrane fouling severely restricts membrane separation efficiency
for wastewater treatment, in 2017, Xu and coworkers fabricated a self-cleaning
wastewater treatment film. Correspondingly, a PDA/polyethyleneimine (PEI)
intermediate layer is fabricated on an ultrafiltration substrate, followed by
mineralization of a photocatalytic layer consisting of photocatalytic β-FeOOH
nanorods [162]. As shown in Figure 5.23, the PDA–PEI layer not only acted
as nanofiltration selective layer but also served as the intermediate layer for
5.5 Conclusion 183
LbL assembly of sodium

silicate and TiO2
Stainless steel mesh
Oil/water separation UV light
Self-cleaning
(a)
120
100
Contact angle (°)
80
60
40
20
0 1 2 3 4 5
(b) Cycle numbers
Figure 5.22 (a) Preparation of a self-cleaning underwater superoleophobic mesh for oil/water
separation by LbL assembly of sodium silicate and TiO2 on a steel mesh. (b) The water contact
angle of the coated mesh could be repeatedly recovered by UV illumination after it was
contaminated by oleic acid. (▴) (silicate/TiO2 )*20 coated mesh; (•) after oleic acid
contamination; (⬧) after UV illumination recovery. Source: Zhang et al. 2013 [163]. Reprinted
with permission of Springer Nature.
anchoring β-FeOOH nanorods through the strong coordination interaction

between Fe3+ and catechol groups. Under visible light, the β-FeOOH nanorod
modified membrane exhibited efficient photocatalytic activity for degrading
organic contaminant through the photo-Fenton reaction in the presence of
hydrogen peroxide, thus showing the self-cleaning property. Moreover, the
modified membrane exhibited good stability and maintained high nanofiltration
performance (≈97.3%) during five photocatalytic filtration cycles.
5.5 Conclusion
Overall, endowing materials with self-healing ability would improve materials’
service life and stability and also would minimize external intervention, includ-
ing monitoring, maintenance, and repairing, during their lifetime of operation.
The field is still at its birth stage, and the applications of the self-healing
UF substrate Visible light

e– H2O2
hν
OH
PDA–PEI codeposition
h+ Dye solution
OH
GA crosslinking OH
Dyes Degraded
products
Photocatalytic
nanofiltration
Fe3+
Hydrolysis
PDA–PEI NFM Mineralized NFM Colorless filtrate
Figure 5.23 Schematic representation of preparation process for the β-FeOOH-mineralized

nanofiltration membrane and its application in photocatalytic nanofiltration. Source: Lv et al.
materials in the environmental domain are limited to membrane filtration,

oil/water separation, and antifouling surface. Thus the application perspectives
of self-healing materials ought to be further explored and expanded to other
environmental processes.
At the state of the art, the following points are noteworthy.
(1) Although some promising advances have been made, there is still a long way
to go to implement self-healing environmental materials in real-world con-
ditions. Moreover, the methods of integrating self-healing agents into base
materials are typically nontrivial, expensive, and time consuming. The envi-
ronmental safety and toxicity of many self-healing agents/materials used in
the environmental processes have not been assessed. The future self-healing
materials that are suitable to practical applications should offer fast healing,
environmental compatibility, and cost effectiveness.
(2) Polymeric self-healing agents are commonly used due to their inherent
flexibility and softness, which, to some extent, discourage their applications
to rigid materials, and the design of high-strength self-healing materials
would break this bottleneck [1]. In 2018, Sun and coworkers have realized
mechanically robust polymer composites with self-healing ability by com-
pounding nitrogen-coordinated boroxine-containing poly(propylene glycol)
with poly(acrylic acid) (PAA) though complexation and hydrogen-bonding
interactions between them [164]. However, this concept is still not applied
in the environmental field, recently.
(3) Computer modeling can provide a deeper and more thorough insight into the
self-healing behavior of polymers and thereby aid the formulation of effective
guidelines for optimizing both the synthesis of these polymers and the design
of the system [165].
(4) Design of self-cleaning materials with the capabilities of self-healing of physi-
cal cracks and/or self-restoration of chemical components would be another
key future research since the self-cleaning components on the surface are
References 185
always fragile and easily damaged when operating in extreme environments

[81, 88].
(5) The recent research about environmental materials with self-healing ability
still remains in its early state. Eventually, it will exist in large volumes
to develop fast, repeatable, and highly effective self-healing materials in
some remarkable field in advanced environmental materials, involving the
self-healable protection of oil pipeline [166], the surface recovery of fog
harvesting [167–169], self-stored photothermal materials [170–173], etc.
The future development direction for the self-healing materials is to further

emulate nature. Bio-inspired self-healing materials have recently developed
as a major branch of intelligent materials, which were designed to recover
mostly mechanical damage or/and surface functions at ambient conditions
without using external stimuli or energy input [1, 8]. With better understanding
the healing phenomenon at the nano- to microscale, more novel self-healing
materials and scalable fabrication strategies could be created. The devices made
from self-healing materials can eventually be functional in severe working
conditions, like deep sea or even outer space. The maintenance and replacement
costs of these devices could also be reduced.
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157

Self-Healing Materials for Environmental Applications

5.1 Biomimetic Self-Healing Materials

Artiﬁcially Intelligent Nanomaterials for Environmental Engineering, First Edition.

5.2 Overview of Self-Healing Materials

5.3 Extrinsic and Intrinsic Self-Healing Materials

5.3.1 Extrinsic Self-Healing Materials

Figure 5.1 (a) Capsule-based healing concept. A microencapsulated healing agent is

5.3.2 Intrinsic Self-Healing Materials

Segmental mobility and

Evolution of damage and repair

Figure 5.2 Schematic illustration of the evolution of an ideal damage-repair process in

Upon structural damage, cleavage of polymer chains leads to the release of

5.4 Self-Healing Materials in Environmental

Figure 5.3 Classiﬁcation of self-healing materials.

5.4.1 Self-Healing of Physical Cracks

of damaged catechol–Fe3+ complexes. Moreover, working as an adsorbent, it

Polyurethane Healed site

(a) Nonwoven fabric

Pristine membrane Damaged membrane Healed membrane

Figure 5.5 (a) Schematic illustration of the self-healing process of microcapsule-embedded

D-clay hydrogel Fe3+ as cross-linker for D-clay

Cross-link with catechol groups (red tetragon)

eﬀectively prevented nonspeciﬁc cell attachment owing to the presence of PEO

(i) Solvent evaporation in moist air (ii) Locking of liquid layer

uPDMS, silicone oil, THF Breath figure

(iv) Rebuilding of liquid layer (iii) Consumption of surface liquid

Silicone oil Gel matrix

5.4.2 Self-Restoring of Surface Functional Components

5.4.2.1 Chemical Mechanism

migration of healing agent can be initiated or accelerated by external stimuli,

5.4.2.2 Hydrophobic Self-Healing

Point-of-use solar distillation device

PPy-coated mesh membrane

6000 n-Hexane 100

Separation efficiency (%)

5.4.2.3 Hydrophilic Self-Healing

PEO brush 3D grafting

water–network interface (Figure 5.15). As a result, the antifouling performance of

crushing Self-healing Protein

5.4.3 Self-Cleaning of Contaminated Surfaces

5.4.3.1 Superhydrophobicity-Induced Self-Cleaning

Contact and move

(a) (b) (c)

“Pick up” NaCl Self-cleaning

(d) (e) (f)

5.4.3.2 Superhydrophilicity-Induced Self-Cleaning

t = 1.12 s after immersion

Under visible light Under UV light

Under visible light Under UV light

the PAAS-m-PAN membrane exhibited an unprecedented antifouling property,

PAA-g-PVDF Copper mesh Nickel foam Nonwoven PP plastic

(e) Coated Uncoated

Figure 5.19 Underwater anti-oil-adhesion and self-cleaning property of PAAS-g-PVDF

Fibrous network: Second-level reentrant structure

Florinated SiNPs CTS/PFO-SiNP

Salt rejection (%)

5.4.3.3 Photocatalytic Self-Cleaning

Figure 5.21 Upon irradiation of ultra-bandgap light, the semiconductor undergoes

LbL assembly of sodium

Oil/water separation UV light

anchoring β-FeOOH nanorods through the strong coordination interaction

UF substrate Visible light

PDA–PEI NFM Mineralized NFM Colorless filtrate