Eg 0

Bioinspired materials for water
supply and management:

rsta.royalsocietypublishing.org
water collection, water
purification and separation of
Review water from oil
Cite this article: Brown PS, Bhushan B. 2016 Philip S. Brown and Bharat Bhushan
Downloaded from https://royalsocietypublishing.org/ on 03 September 2021
Bioinspired materials for water supply and

management: water collection, water Nanoprobe Laboratory for Bio- and Nanotechnology and
purification and separation of water from oil. Biomimetics (NLBB), The Ohio State University, 201 W. 19th Avenue,
Phil. Trans. R. Soc. A 374: 20160135. Columbus, OH 43210-1142, USA
http://dx.doi.org/10.1098/rsta.2016.0135
PSB, 0000-0001-5390-5098; BB, 0000-0001-7161-6601
Accepted: 21 April 2016 Access to a safe supply of water is a human right.

However, with growing populations, global warming
One contribution of 12 to a theme issue and contamination due to human activity, it is one that
is increasingly under threat. It is hoped that nature can
‘Bioinspired hierarchically structured surfaces
inspire the creation of materials to aid in the supply
for green science’. and management of water, from water collection
and purification to water source clean-up and
Subject Areas: rehabilitation from oil contamination. Many species
nanotechnology, materials science, biomedical thrive in even the driest places, with some surviving
engineering, physical chemistry on water harvested from fog. By studying these
species, new materials can be developed to provide
Keywords: a source of fresh water from fog for communities
biomimetics, water, fog harvesting, across the globe. The vast majority of water on the
Earth is in the oceans. However, current desalination
desalination, purification, separation
processes are energy-intensive. Systems in our own
bodies have evolved to transport water efficiently
Author for correspondence: while blocking other molecules and ions. Inspiration
Bharat Bhushan can be taken from such to improve the efficiency of
e-mail: bhushan.2@osu.edu desalination and help purify water containing other
contaminants. Finally, oil contamination of water from
spills or the fracking technique can be a devastating
environmental disaster. By studying how natural
surfaces interact with liquids, new techniques can be
developed to clean up oil spills and further protect our
most precious resource.
This article is part of the themed issue ‘Bioinspired
hierarchically structured surfaces for green science’.
2016 The Author(s) Published by the Royal Society. All rights reserved.
1. Introduction 2
‘The human right to water entitles everyone to sufficient, safe, acceptable, physically accessible
rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

.........................................................
and affordable water for personal and domestic uses’ [1].
Water is a vital resource upon which our survival depends. Water covers 70% of the Earth’s
surface; however, at any one time the vast majority of water is contained in the oceans, with
fresh water accounting for only 2.5% of all water (figure 1a). Water continuously moves in a cycle
because of evaporation, condensation, precipitation, surface and channel run-off, and subsurface
flow (figure 1b). The evaporative phase can help purify water by separating it from contaminants
picked up in other phases of the cycle, including salt in the oceans. Of the 2.5% fresh water, the
majority is trapped as glaciers and snow (1.74% in total) while only 0.79% (11 quadrillion cubic
metres) of all water is found in lakes, rivers and as groundwater (which itself accounts for 0.76%
in total; figure 1a) [2]. The distribution of this water is not uniform across the world, with around
20% of the world’s surface fresh water found in the North American Great Lakes [3].
With global warming leading to increased drought periods, it is becoming apparent that our
current supply of fresh water must be supplemented if our future needs are to be met. Global
water consumption is expected to reach 6 trillion cubic metres a year by 2030 as the population
moves towards a projected 8.2 billion [4,5] (figure 2). These challenges will mean that more fresh
water sources will be under increased stress as demand outstrips supply (figure 3a). The number
of people living in areas affected by severe water stress is expected to increase from 2.8 billion
in 2005 to 3.9 billion by 2030, representing over 47% of the projected population [4]. While the
majority of these people will live in South Asia, the Middle East and North Africa, global warming
will probably offset efficiency gains made in industrial sectors in countries such as the United
States.
In addition, despite progress during the last decade thanks to the ‘UN Water for Life’ initiative,
access to water also remains an issue for some of the poorest countries, with 1 in 10 people still not
having access to an improved water source (figure 3b). An improved water source is defined as
one likely to be protected from outside contamination, and includes water piped into a dwelling
or yard, public tap, borehole, protected dug well, protected spring and collected rainwater [7].
However, although a water source may be classified as ‘improved’, it is not necessarily safe
for human consumption [8]. There are still many people in the world who do not know where
their next drink of clean water will come from. These communities stand to benefit the most
from advances in the science and engineering of materials and devices for water supply and
management.
All living things require water. Therefore, it is no surprise that, after some 3 billion years
of evolution, many species exhibit efficient solutions to ensure their water security [9]. These
solutions typically involve species possessing unique chemistry and structuring on or within their
body that help to dictate the movement of water.
For instance, many plant and animal species in arid regions rely on their ability to collect
water from fog. By studying the chemistry and structures involved, it is possible to create artificial
fog harvesters to provide a supplemental water source for communities in regions where fog is
common, such as coastal regions of the western United States, South America and western Africa.
Another source of water would be the saline water found in the oceans, which account
for over 96.5% of all water on the planet (plus a further 1% found in brackish groundwater).
However, water purification, especially desalination, where saline water is made fit for human
consumption [10], remains an energy-intensive process [11]. Systems in our own body are capable
of filtering water, removing organics and ionic species with high water permeabilities and at low
energy cost. Incorporation, adaptation or replication of the biological structures involved could
enable creation of more efficient water purification membranes for the conversion of seawater
into a regular source of fresh water. Purification membranes can also help to ensure that other
sources of water remain safe for human consumption.
Finally, in an age of high-profile industrial accidents such as the Deepwater Horizon in the
Gulf of Mexico, in addition to contamination of groundwater sources due to unsafe oil disposal
(a)
3
0.001%
atmosphere

.........................................................
0.03%
surface
1.74% water
glaciers and snow
96.5%
oceans
0.76%
groundwater
1%
brackish
groundwater
97.5% 2.5%
saline water fresh water
data from [2]
(b)
cloud formation
condensing water vapour

precipitation snow
evaporation surface run-off
lakes
ocean channel run-off

salt water groundwater
intrusion river penetration
subsurface flow
impervious layer
Figure 1. (a) Percentage breakdown of all water on the Earth. Fresh water represents 2.5%, with surface water in rivers and
lakes only accounting for 0.03% (400 trillion cubic metres) of all water. (b) The water cycle, where the evaporative phase helps
purify water via separation from contaminants picked up in other phases of the cycle.
practices, it is important to protect sources of water from human activities. Oil spills cause untold
damage to the environment in addition to potentially contaminating sources of potable water.
Furthermore, there has been an increase in the use of hydraulic fracturing or ‘fracking’ to extract
oil in the United States. This results in large amounts of wastewater that must be processed to
remove oil contamination before being released back into the water supply. We can study natural
surfaces such as the lotus leaf to learn how nature interacts with water and oils, and adapt this to
create devices capable of separating the two liquids.
actual projected
water consumption (1012 m3 yr–1)

6 4
5

.........................................................
4 global
3
Asia
2
1 Oceania Africa Americas

Europe
0
1980 1985 1990 1995 2000 2005 2010 2015 2020 2025 2030
actual data from [6] year
projected data from [5]
Figure 2. Actual (1980–2010) and projected (2030) global water consumption.
(a)
no water stress low water stress

moderate water stress severe water stress
data from [4]
(b)
>95% 83–95%
65–83% <65%
no data
data from [7]
Figure 3. (a) Projected water stress by 2030 when an estimated 47% of the world’s population will live in areas of extreme
water stress and (b) percentage population with access to improved water source in 2015, as defined by WHO/UNICEF.
By altering the chemistry and topography of a surface, with inspiration from nature, it
5
is possible to change how droplets of water and other fluids interact with that surface (see
appendix A) [9,12,13]. And, as detailed later, by creating a heterogeneous surface with areas

.........................................................
where the water affinity is different, it is possible to dictate the direction in which water droplets
move, even against gravity. In this review, we will discuss how nature has evolved chemistry and
structures to manipulate water. By studying these examples, it is hoped that new solutions can be
developed to help in water collection, water purification and separation of water from oil.
2. Collecting water
Air is a potential source for water. Fog is a mass of micrometre-sized water droplets that form
when air becomes saturated with water vapour. The size of the droplets means they float in the
air and deposit onto a surface as a result of either settling or interception. Fog can be a vital source
of water, particularly in arid areas that receive little rainfall.
It would be beneficial for populations in these arid regions to develop a means to harvest fog
directly from the air. Such ideas are by no means new. In fact, there is evidence that suggests
hunter–gatherer groups were able to populate arid areas along the southern coast of Peru by
using fresh water from fog over 5000 years ago, though the collection method is unknown [14].
Today, a common method for fog interception and harvesting uses nets which are able to provide
a supplemental source of water in arid regions across the globe (figure 4). Charities such as
FogQuest have installed polymer nets in Central and South America, Africa and South Asia. In
addition, to overcome the limitations of a two-dimensional net, new designs are being developed,
such as a tower by the charity Warka Water. However, the nets in these devices are typically made
of material that has not been optimized for water collection.
Several animal and plant species have evolved surface structures and chemistries that enable
them to collect water from fog (figure 5). These include Namib Desert beetles, several lizard
species, spider webs and various types of cacti, grasses and other plants. These species (or, in
the case of spider webs, external structures built by a species) typically feature areas where fog
droplets can deposit and grow before eventually being transported either towards mouths, in
the case of animals, or a region that absorbs water, in the case of plants, such as the roots. In this
section of the review, we will highlight the species capable of harvesting fog and highlight several
methods employing biomimicry and bioinspiration to aid in water collection from fog.
(a) Namib Desert beetles

Stenocara gracilipes and Onymacris unguicularis are beetles native to the Namib Desert in southern
Africa. The region is one of the most arid in the world, with average annual rainfall of only 1.8 cm,
and it is not uncommon to experience consecutive years with no rainfall at all [24]. However,
the area is not devoid of life, with several species of flora and fauna seemingly thriving. It was
postulated that the ability to survive in this climate was the result of collection of water from fog.
Despite the low rainfall, prevailing southwesterly winds form fog along the coast 60–200 days per
year, which can be blown up to 50 km inland [24]. The first observation of fog harvesting in the
Namib Desert was in 1976, with beetles emerging during nocturnal fogs and lowering their heads
while oriented into the wind (figure 5) [25]. The water was found to trickle down the body of the
beetle and into the mouth. By weighing the beetle before and after fog harvesting, it was found
that a gain of over 30% in total body weight was possible after harvesting.
In 2001, the mechanism for fog collection was uncovered [16]. It was discovered that the
back of the beetle comprised a random array of 0.5 mm diameter bumps spaced 0.5–1.5 mm
apart (figure 5). The bumps were found to be smooth, while the surrounding area was covered
in microstructured wax. Water from the fog is observed to land on the bumps and droplets
begin to grow. The droplet continues to grow (up to 4–5 mm) until the weight of the droplet
overcomes the capillary force and the droplet detaches and rolls down the tilted beetle’s back.
It was hypothesized that the bumps are hydrophilic (water loving, see appendix A), while the
(a) (b) 6

.........................................................
5 mm
Figure 4. Commercial net-based water collectors currently available from (a) FogQuest (photograph by Anne Lummerich,
inset: adapted with permission from [15]. Copyright 2013 American Chemical Society) and (b) Warka water (photograph
by Architecture and Vision).
background wax is hydrophobic (water fearing). To confirm that an array of hydrophilic bumps
on a hydrophobic background is indeed responsible for the fog harvesting, the researchers created
a model surface comprising 0.6 mm glass beads fixed in wax. This surface was found to collect
more water than the wax or glass surfaces taken alone [16].
Attempts to mimic the patterned back of the beetle to create fog collectors have been
undertaken (figure 6). Hydrophilic polymers have been deposited through a mask via plasma
deposition onto a superhydrophobic polymer substrate (figure 6a) [26]. Both the wettability
of the hydrophilic spots and the pattern dimensions were investigated. It was found that, on
hydrophilic spots with diameters less than 400 µm, water droplets were unable to grow to a size
sufficient for their weight to overcome the surface tension. However, this was only investigated
for one plasma-deposited polymer; therefore, this threshold value may be different for different
wettabilities. It was found that the poly(4-vinylpyridine) spots resulted in the highest water
collection rate. However, the 4-vinylpyridine monomer used in the process to create the plasma-
deposited polymer is extremely toxic and the masked plasma deposition process is not suitable
for mass production. In addition, polymers deposited onto superhydrophobic substrates may
suffer from poor interfacial adhesion. Unfortunately, no durability studies were carried out.
Similarly patterned surfaces have also been created using inkjet printing [30]. In this case, the
stability of the micropatterns was tested to ensure good adhesion of the hydrophilic spots to the
superhydrophobic substrate.
Another study used hydrophilic steel needles soldered to a cooled copper block and pierced
through a superhydrophobic film (figure 6b) [27]. Water droplets were found to condense and
grow on the tips of the cooled steel needles before rolling over the superhydrophobic film once
they reached a certain weight (figure 7a). The study focused more on the condensation of water
from humid air and employed the cooling stage throughout. However, because the needle tips
are hydrophilic, it could also be used in fog collection, although the tip diameter may need to be
increased to aid attachment of the larger droplets in fog.
One fog-harvesting device that is relatively easy to fabricate consists of a wire mesh pressed
into a polymer sheet (figure 6c). Copper wire mesh was first calcined to create a copper oxide
layer featuring surface structures on the nanoscale. This, when combined with a fluorinated
thiol treatment, resulted in a superhydrophobic material. The mesh was then pressed into a
heated polystyrene (PS) sheet to create a composite surface with heterogeneous wettability [28].
Different mesh sizes were investigated, with the most efficient material demonstrating a water
collection rate of 160 mg cm−2 h−1 . This technique is slightly different from others in that the
patterned surface features hydrophilic wells surrounded by the hydrophobic wire mesh, instead
of hydrophilic bumps surrounded by hydrophobic valleys. By varying the temperature of the
sample during pressing, the depth of the wells was varied and this was found to be an important
Species Mechanism Comments 7
water droplets grow on
hydrophobic wax-free hydrophilic bumps

.........................................................
before being transported
towards the mouth by the waxy
hydrophilic hydrophobic surround [16]
Stenocara gracilipes (beetle)

a hydrophilic surface supports
a thin water film and capillary
Animal
action directs water through

asymmetric channels, favouring

transport towards the mouth [17]
Moloch horridus (lizard)
knot due to Laplace pressure and

surface energy gradients, water
droplets move along hydrophilic
silk towards knots [18]
Araneae (spider web)

water droplets grow on tips of
barb small barbs before moving
spine down onto spine and travelling
towards base, due to Laplace
pressure and surface energy
gradients, where they are
Opuntia microdasys (cactus) absorbed [19]
water droplets are channelled

down the hydrophilic leaves
Plant
towards the base of the plant

and eventually reach the
roots [20–22]
Stipagrostis sabulicola (grass)
water droplets grow on tiny

hairs before dropping down
further into the plant structure
when they get too heavy and
eventually reaching the roots [23]
Cotula fallax (bush)
Figure 5. Summary of animal and plant species found to collect water from fog. A combination of chemistry and structuring
results in interception of water from fog and transport to the mouth, roots or another area where it can be used.
factor in the amount of water collected, though the details of the droplet removal mechanism
from these surfaces require further study.
Another study involved the dewetting of polymer to create hydrophilic areas atop
a hydrophobic background (figure 6d). Hydrophilic poly(2-hydroxypropyl methacrylate)
(PHPMA) was spin coated on top of hydrophobic PS [29]. Thermal annealing of the bilayer above
the glass transition temperature of the PHPMA led to dewetting of the top layer and the formation
of hydrophilic domains on top of the hydrophobic PS. By varying the molecular weight of the
PHPMA polymer, the size of the domains could be altered. When exposed to fog, droplets were
(a) (b) 8
CF4-treated polymer PGMA + NH2-PS
PE + Si-NP steel needles
(hydrophobic) (hydrophilic)

.........................................................
(superhydrophobic) (hydrophilic)
silica aerogel copper block

(insulation) (heat sink)
1 mm
(c) (d )
polystyrene PHPMA
(relatively hydrophobic) (hydrophilic)
polystyrene CuO-PFDT
(relatively hydrophilic) (superhydrophobic)
Figure 6. Summary of various techniques for fabricating beetle-inspired water collectors: (a) plasma-deposited hydrophilic
spots atop hydrophobic polymer (adapted with permission from [26]. Copyright 2007 American Chemical Society);
(b) hydrophilic steel needles pierced through superhydrophobic film (adapted with permission from [27]. Copyright 2015
American Chemical Society); (c) superhydrophobic copper mesh pressed into hydrophilic (relative to the copper mesh) polymer
sheet [28]; and (d) dewetted hydrophilic polymer regions atop a hydrophobic (relative to the hydrophilic polymer regions)
polymer (adapted with permission from [29]. Copyright 2015 American Chemical Society).
observed to grow on the hydrophilic domains (figure 7b). However, measuring less than 10 µm in
size, the hydrophilic domains are much smaller than the spots on the beetle and, depending upon
the molecular weight, are interconnected. While water droplets were found to attach and grow
on these hydrophilic domains, the shedding mechanism of these droplets is quite different from
that of the beetle. It is estimated that a droplet of sufficient size to detach from the surface will be
in contact with tens of thousands of hydrophilic domains. Successful droplet shedding was not
demonstrated in the paper. This step is vital as the droplets need to detach in a timely manner so
new droplets can begin to form on the vacated hydrophilic regions.
Biomimetic fog-harvesting surfaces based on the patterned surface of the beetle have also
been created via a patterned hydrophilic polyelectrolyte array [31] and patterned nanograss [32].
However, these studies did not fully investigate the water-collecting ability of these surfaces.
(b) Lizards
Moloch horridus is a species of lizard native to arid regions in western and southern Australia
(figure 5). It was first believed that the lizard absorbed water through its skin. However, research
in the 1960s discovered that, instead, water droplets spread out over the skin before reaching the
mouth [33]. The movement of the water was attributed to capillary action along open channels in
the skin. Similarly, when water was added to the bodies of Phrynocephalus helioscopus, a species of
(a)
0.03 h 2.80 h 9

.........................................................
needle
tip 2 mm
CA ~ 168 ± 2°
(b)
water 1s 20 s
droplets
hydrophilic
regions
hydrophobic
background
10 mm
100 s 150 s
Figure 7. Time-lapse images showing water droplet growth on beetle-inspired (a) hydrophilic steel needles pierced through
superhydrophobic film (adapted with permission from [27]. Copyright 2015 American Chemical Society) and (b) dewetted
hydrophilic polymer regions atop a hydrophobic polymer (adapted with permission from [29]. Copyright 2015 American
Chemical Society).
lizard native to arid regions in Asia, the lizard adopted a posture where the head was depressed
and the hindquarters were elevated, which helped guide the water to the mouth [34].
A more recent study of numerous species of lizards found that several exhibit water-harvesting
potential [35]. The study of one lizard in particular, Phrynosoma cornutum or the Texas horned
lizard, found that water placed on the skin flowed preferentially towards the mouth, with
capillary forces dominating over gravitational and viscous forces (figure 8) [17]. Examination
revealed a network of capillary channels and found that there was a narrowing of individual
channels in the direction of the mouth (longitudinal) (figure 5). An abrupt widening from one
channel to the next, in addition to an interconnecting narrower channel running laterally, would
follow. The narrowing of the channel results in favourable water transport in that direction due
to the curvature of the liquid–air interface. The lateral interconnecting channels overcome the
effects of the abrupt widening and help maintain an advancing liquid front [17]. In the backward
direction, liquid flow is stopped as the channel widens and pressure would need to be applied to
force the liquid in that direction. In addition to water transport for water collectors, the authors
hypothesized that channels that allow liquid flow in one direction but inhibit flow in the other
direction could find use in microfluidic and medical applications. However, no artificial surfaces
based on the structure of the lizard for water collection have yet been created.
(c) Spider webs

Spider silk has been well studied as a fibre with excellent mechanical characteristics. This natural
material comprises proteins and outperforms many synthetic materials with regards to strength
and elasticity [36]. Spider webs are also known to collect water, as evidenced by the many
photographs capturing a dew-glistened web (figure 5). Dry webs undergo moisture-induced
snout +26% 10

.........................................................
0s 1.6 s
+48% +70%
3.3 s 5.0 s
Figure 8. Time-lapse images showing directional spreading of water droplets deposited on lizard skin. Preferential water
transport occurs towards the snout [17].
spindle knot joint

(a)
200 mm
(b)
30 mm
(c) stretched porous structure (d) random porous structure
1 mm 1 mm
(e) t = 7.708 s ( f ) t = 7.955 s (g) t = 8.116 s
t = 8.427 s t = 8.588 s t = 8.717 s

(h) (i) (j)
100 mm
Figure 9. (a) Image of spider webs, after water-induced structural changes, comprising thick knots connected by thinner joints
due to Rayleigh instability; (b–d) SEM images showing morphology of knot and joint; and (e–j) time-lapse images showing
preferential transport of water droplets from joints to knot. (Reproduced with permission from [18]. Copyright 2010 Macmillan
Publishers Ltd.)
structural reorganization. First, the hygroscopic nature of the proteins contained within the silk
results in the condensation of water droplets and the swelling of the cylindrical silk thread. This
cylinder is then broken up because of Rayleigh instability, where a cylinder of fluid will break
up into smaller drops to lower its surface area, resulting in the formation of a ‘beads on a string’
structure with a series of knots periodically spaced along the thread (figure 9a) [37]. It is thought
this rebuilding of the web structure and subsequent water capture is beneficial for the spider, as
not only does it provide a source of drinking water, but it also results in improved capture of prey
due to the water-swollen knots possessing enhanced adhesive properties [37].
Analysis of the wet-rebuilt web using scanning electron microscopy (SEM) revealed that the
11
knots were composed of randomly oriented porous nanofibrils, while the interconnecting joints
were composed of stretched porous nanofibrils aligned parallel to the thread (figure 9b–d) [18].

.........................................................
When water condensed on the wet-rebuilt spider thread, the droplets condensing on the joints
were found to move to the knots (figure 9e–j). This is thought to be because of a combination of
a surface tension gradient due to the knots displaying a rougher surface thanks to the randomly
oriented nanofibrils (the roughness enhances their hydrophilicity as the droplets are in the Wenzel
state of wetting, see appendix A), and a Laplace pressure gradient due to the higher radius of
curvature of the joints compared with the larger knots [18].
For a droplet resting on such a fibre, the changing fibre radius (r) results in a pressure difference
inside the droplet. At low fibre radius, the droplet shape (where h is the height of the droplet) is
hardly deformed by the fibre (as r < h) and is near spherical (P = 2γ /h, where γ is the surface
tension). As the fibre radius is increased, h tends towards r and the droplet becomes flatter (P =
γ /r). This flattening results in a lower Laplace pressure and droplets therefore move on a conical
fibre from regions of low radius to regions of higher radius [38].
The combination of this Laplace pressure gradient and the surface tension gradient results
in the transport of droplets towards the knots (figure 5). Even micrometre-sized droplets were
observed to move, despite the increased importance of contact angle hysteresis effects at this
scale (see appendix) [18].
Many of the attempts to replicate the spider web use the same Rayleigh instabilities that
dictate its structure. For instance, nylon fibres immersed in a poly(methyl methacrylate) (PMMA)
solution [39] were removed to leave a thin, cylindrical film of the polymer solution on the fibre.
This then spontaneously broke up into regularly spaced knots because of the Rayleigh instability
(figure 10a). The fibres were then treated with a second polymer solution to alter the chemistry
and roughness of the knots. By altering the polymer and solvents used, the knots could be
functionalized with a variety of surface energies and levels of roughness, respectively, with the
joints remaining unchanged. It was found that when smooth hydrophobic knots were created,
droplets could be driven from the knots onto the hydrophilic interconnecting joints, which is
the opposite direction to that found on the spider web. This was due to the surface energy
gradient being able to overcome the Laplace pressure force gradient. When the hydrophobic
knots were rough, the droplets would travel towards the knots as hysteresis resistance prevents
the droplet from following the surface energy gradient and instead the Laplace pressure force
gradient dictates the movement of the drops [39]. The same group also investigated the effect of
polymer concentration and the velocity of removing the nylon thread from solution, which were
both found to alter the size of the knots [42]. Threads with larger knots were found to display
increased water collection abilities.
Bioinspired fibres have also been created via coaxial electrospinning (figure 10b). PS and
PMMA solutions were electrospun together forming a fibre with a PS inner and a PMMA outer
shell [40]. The dilute nature of the PMMA solution means the Rayleigh instability is able to
overcome the viscous forces and this results in a thread composed primarily of PS with knots
of PMMA evenly distributed along its length. Water collection experiments found that droplets
travelled towards the knots because of a combination of the surface energy gradient and Laplace
pressure gradient.
While the knots on spider webs can help to coalesce and grow water droplets on the thread,
there is no transport of the droplets over larger distances. It was found that dipping and
withdrawing a thread in a polymer solution at a fixed angle could vary the size of the knots
formed across the thread (figure 10c) [41]. It was found that the thread was able to transport
a droplet in the direction of increasing knot size, which the authors attribute to a continuous
change in the Laplace pressure and droplet coalescence. Despite the promise of improved water
transport, the use of bioinspired threads for water collection still faces challenges. Many studies
focus on the water collection properties of a single thread and do not attempt to create a larger
device. Additionally, the thin threads being studied may not be durable enough to withstand the
extreme environments where fog collection would be beneficial. Finally, although some progress
(a)
12
(i) PMMA Rayleigh
(ii) PVAc/PS/PVDF break-up PMMA PMMA/PVAc/PS/

.........................................................
(DMF + ethanol) joint PVDF knot
nylon fibre
(b)
PMMA PS
PMMA
solution
PS
solution
(c)
PVDF
nylon fibre
q
PVDF/DMF
solution
Figure 10. Summary of various techniques for fabricating spider web-inspired water collectors using the Rayleigh instability
to form knot and joint structures: (a) dip-coated polymer threads with various chemistries and roughness [39]; (b) electrospun
polymers featuring hydrophilic knots (reproduced with permission from [40]. Copyright 2012 John Wiley & Sons, Inc.); and
(c) tilt-angle dip-coated threads featuring knots of various sizes allowing for preferential water transport in one direction
(reproduced with permission from [41]. Copyright 2013 Macmillan Publishers Ltd).
has been made, the full mechanism of water transport/shedding for efficient water collection is
not yet clear.
(d) Cacti
Cacti are commonly found in areas of drought. Therefore, they are mostly succulents, a type of
plant with thick, fleshy and swollen parts that are adapted to store water and minimize water
loss [43]. The first example of a cactus species using fog as a supplemental source of water was
reported in the 1970s [44]. Copiapoa haseltoniana, a species native to the Atacama Desert, was found
to use the run-off from nightly fog events to survive in what is the driest non-polar desert in the
world [45]. More recently, Gymnocalycium baldianum, a species in neighbouring Argentina, was
found to collect and transport water through microcapillaries [46].
Opuntia microdasys is a species of water-collecting cactus endemic to Mexico, which features
small barbs atop conical spines that help in the collection of water [19] (figure 5). Water collects
on the small barbs and moves onto the spine as the droplets grow. Once on the spine, the droplets
move towards the base due to a combination of surface energy and Laplace pressure gradients.
Once at the base of the spine, the plant absorbs the water.
In an attempt to mimic the water collection ability of cacti, copper wires were gradually
dipped into an electrochemical corrosion solution to form a conical shape [47] (figure 11a). Gold
(a)
13

copper
.........................................................
copper
wire
1-DDT
(b)
PDMS LDPE mold
cones replica
PDMS
(c)
stem wire
Si
substrate catalyst (ZnO)
branched ZnO
wire
Figure 11. Summary of various techniques for fabricating cactus-inspired water collectors: (a) dip-coated conical copper wires
with gradient wettability (reproduced with permission from [47]. Copyright 2013 John Wiley & Sons, Inc.); (b) hexagonally
arranged moulded PDMS cones for increased fog interception (reproduced with permission from [48]. Copyright 2014 John
Wiley & Sons, Inc.); and (c) vapour-deposited hierarchical zinc oxide wires for droplet coalescence (reproduced with permission
from [49]. Copyright 2014 American Chemical Society).
nanoparticles were then electroplated onto the copper wire to allow for thiol attachment. Finally,
the conical copper wire was chemically modified by being gradually dipped into a thiol solution,
resulting in a gradient wettability. This gradient wettability was found to result in improved
water collection compared with uniformly hydrophilic or hydrophobic wires, suggesting that the
Laplace pressure gradient alone is not enough to drive water transport efficiently.
In another study, in order to create an array of conical objects, a stainless steel needle was used
to punch holes into a polymer sheet (figure 11b). Polydimethylsiloxane (PDMS) was then added
to create a negative image, resulting in an array of PDMS cones [48]. It was found that water
collection was much greater when the cones were positioned in a hexagonal arrangement due to
increased interception of water droplets from the fog.
Another cactus-inspired design involved the use of branched zinc oxide (ZnO) wires
(figure 11c). The structure was created by reacting zinc vapour with oxygen at 950◦ C over a
silicon substrate, which results in the creation of branched, conical ZnO wires [49]. For the
water collection experiments, the branched ZnO structure must be flipped so the section directly
attached to the silicon substrate becomes the tip, where the water droplets are then collected. They
are then able to move along the main conical stem, as it increases in diameter, due to the Laplace
pressure gradient. The branched structure formed near the base of the main stem was found
14
to collect additional water, which penetrated into the gaps between the branches and coalesced
with the droplets travelling from the tip. The water collected at the base of the stem was then

.........................................................
removed by syringe. Although these experiments demonstrated the water collection ability of
these structures, they would seem to be unfeasible for fabrication of a viable water collection
device. The ZnO structures would need to be manually removed, flipped and re-attached to the
substrate. Additionally, the durability of these delicate structures has not been studied. It is also
not clear if the water can be removed from the base of the main stem without the use of external
pressure.
(e) Other plant species

Other plant species adapted to collect water from fog include Stipagrostis sabulicola, a grass
endemic to the Namib Desert. First studied in 1980, water droplets are observed to collect on
the leaf before coalescing and running down towards the base of the plant [20,50]. The leaves
feature longitudinal ridges, which dictate this fluid flow (figure 5) [21]. Another type of grass,
Setaria viridis, is found to collect water with a similar structure and mechanism to that found on
the Opuntia microdasys cactus [51].
Another plant studied for water collection from fog is Cotula fallax, which is native to South
Africa. Fine hairs on the leaves of the plant intercept fog droplets where they coalesce and grow
before dropping down through the plant structure when they become too heavy (figure 5) [23].
This fog-harvesting mechanism allows efficient collection of water from multiple directions,
unlike other two-dimensional structures such as those based on the beetle back.
(f) Outlook
Of all the bioinspired fog harvesters reviewed here, using patterned heterogeneous surfaces
based on the beetle back is perhaps the most common method. However, challenges here still
remain. Although several papers have demonstrated that hydrophilic spots deposited on top of
hydrophobic or even superhydrophobic backgrounds are able to collect water from fog, the long-
term durability of these materials has not been fully investigated. For instance, the deposition
of such islands upon low-surface-energy films may result in poor interfacial adhesion, and
therefore low mechanical durability. The issue of durability is particularly important given that
fog harvesters will be required in remote regions where regular maintenance is not possible,
or areas prone to extreme conditions such as high diurnal temperature variation and abrasion
from sand.
The lessons learned from different natural surfaces can also be combined to enhance
water collection on bioinspired surfaces. For instance, a patterned heterogeneous surface with
hydrophilic spots on a hydrophobic background—as inspired by the beetle back—can be
modified to include hydrophilic star shapes in place of circular sports, as inspired by spider
webs (figure 12). Bai et al. [52] found that surfaces featuring stars were more efficient at collecting
water than those with circular spots. The authors attributed this to the Laplace pressure gradient
resulting in a droplet being transported more efficiently from one of the tips of the star into the
centre, leaving the area clear for collection of new droplets [52].
In terms of fabricating a water collection device, cactus-inspired structures are favourable
as they can use surface energy and Laplace pressure gradients to drive droplets in a specific
direction. This contrasts with most designs inspired by spider webs in which droplet transport
is to the nearest knot where it must remain until it grows sufficiently in size to detach. Cactus-
inspired designs also have advantages over those based on the beetle back as three-dimensional
structures can be created to increase the surface area, which gives rise to increased droplet
interception.
(a) circle-shaped 15
pattern

.........................................................
100 mm
(b) star-shaped
pattern
100 mm
Figure 12. Time-lapse images showing water droplet growth on: (a) beetle-inspired circle pattern and (b) hybrid beetle- and
spider-inspired star pattern, which results in greater collection due to more favourable droplet transport and coalescence.
(Reproduced with permission from [52]. Copyright 2014 John Wiley & Sons, Inc.)
polymer net bioinspired net
bioinspired
conical
structures
wind
direction
polymer
mesh
woven polymer net provides surface for nets featuring cactus-inspired conical structures
interception of fog droplets, but surface chemistry increase surface area available for droplet
and structuring not optimized to facilitate interception and help facilitate efficient droplet
efficient droplet coalescence, movement and coalescence and movement, resulting in a
collection greater amount of water collected
Figure 13. Comparison of water-collecting nets. Existing polymer net is not optimized for droplet coalescence and movement.
Bioinspired nets feature structures and chemistries that enable efficient interception, coalescence and movement of droplets
for increased water collection.
The lessons learned from natural fog collectors are already being applied to the more
traditional fog harvesters currently used. For instance, polyolefin meshes with bioinspired
wettabilities have shown increased water collection efficiency compared with the untreated
meshes [53]. Figure 13 demonstrates how cactus-inspired structures can be incorporated into
a fog-collecting mesh. Meshes featuring both conical barbs inspired by cacti and microgrooves
inspired by grasses have also been proposed [54]. However, challenges remain for these devices.
In many cases, the conical structures are likely to be very delicate and may not be suitable for the
challenging conditions where fog collection would be needed most.
3. Purifying water
Water purification is important to ensure more conventional sources of water are free from
contaminants. After the city of Flint, MI, USA, changed its water to a source where corrosion
control treatments had not been applied, the more corrosive water caused lead to leach from the
osmosis reverse osmosis
16
external
pressure

.........................................................
osmotic H2O
pressure
H2O
Na+
Cl–
semipermeable semipermeable
membrane membrane
water moves through semi- external pressure is applied to

permeable membrane into region overcome osmotic pressure,
with higher salt concentration in an causing water to move through
attempt to equalize solute semipermeable membrane to
concentrations on both sides region with lower salt concentration
Figure 14. Schematic showing the differences between osmosis and reverse osmosis. In osmosis, water travels across a
semipermeable membrane to equalize solute concentrations. In reverse osmosis, external pressure is applied to prevent water
travelling into regions of higher solute concentration and additional pressure instead causes water to travel into regions of lower
solute concentrations.
ageing pipe network, culminating in a serious threat to public health [55]. The change has also
been linked to an outbreak of Legionnaires’ disease, a type of pneumonia caused by bacteria [56].
Proper water purification could prevent such contaminants from reaching human consumers.
When it comes to purifying water, there are numerous techniques available, including the use
of adsorbents such as activated carbon [57], biomaterials [58] and zeolites (porous minerals) [59]
to remove organics from wastewater. However, the use of adsorbents has its downsides, such as
inefficiencies due to contaminant removal and regeneration of the adsorbent.
Ultraviolet treatments have also been used to disinfect water [60], and can be combined with
metal oxide catalysts for improved oxidation rates. However, the use of ultraviolet light cannot
remove heavy-metal or other non-living contaminants, and the process can be expensive and
ineffective on cloudy or turbid water.
Conventional purification techniques typically involve membranes and the separation of
contaminants. There are two mechanisms that dictate water transport through a membrane,
both of which can occur together. One mechanism is solution–diffusion, where water molecules
dissolve into the membrane and diffuse through the membrane to desorb from the other side.
Another mechanism is pore flow, where the size of the pores is smaller than the contaminant
being removed [61]. Membranes are typically polymeric in nature, but there are examples of
ceramic membranes composed of materials such as alumina, titania and silicon carbide, for high-
temperature applications. Nanomembranes made of graphene [62] or etched silicon [63] are also
being developed.
One potential source of water is the oceans, which account for 96.5% of all water on the
planet [2]. However, in terms of human consumption, ocean water is contaminated by salts, as
well as by bacteria and particulates. To make ocean water fit for human consumption, it must first
be desalinated and purified [10].
For desalination, a common technique is reverse osmosis. Normally, if two aqueous solutions
with varying solute concentrations are placed either side of a semipermeable membrane, water
will move through the membrane from a region of low solute concentration to a region
of higher solute concentration in an attempt to equalize the concentrations (figure 14). This
process is known as osmosis and the tendency for a solution to take in water is defined as
the osmotic pressure. In reverse osmosis (RO), external pressure is applied to overcome this
osmotic pressure, preventing the flow of water into the region of higher solute concentration.
microporous mesoporous macroporous 17

.........................................................
0.1 nm 1 nm 10 nm 100 nm 1 mm 10 mm
oil emulsions
target water colloidal solids
solute
proteins bacteria
ions viruses
natural
porous aquaporins surface bacterial eggshell
material layer threads

proteins
bioinspired carbon nanotubes
porous pore- block copolymers
material forming
molecules templated metal oxides
0.1 nm 1 nm 10 nm 100 nm 1 mm 10 mm
Figure 15. Comparison of length scales of target solutes, natural porous materials and bioinspired porous materials.
Additional pressure above the osmotic pressure will instead cause water to move into the
region of lower solute concentration (figure 14). The requirement for this applied pressure
means that separation via an RO membrane can be energy-intensive, consuming at least
2 kWh m−3 [10], whereas the theoretical minimum energy required for desalination should be
around 1 kWh m−3 [11]. This excess pressure is due to the low permeability of the membranes
involved. A membrane with low water permeability will require additional applied pressure
above that required to balance the osmotic pressure in order to result in reasonable water
fluxes [11]. Therefore, biomimicry is an appealing alternative, as nature has examples of
membranes with higher separation rates and permeabilities than man-made equivalents. In this
section of the review, we will focus on methods that employ biomimicry and bioinspiration to aid
in water purification.
The focus of many studies of bioinspired membranes is typically porous materials for
nanofiltration and RO applications. Porous materials are classified into three main categories
depending upon their pore size. For instance, microporous materials contain pore diameters less
than 2 nm, which are required for desalination. However, ocean water (and other water sources)
can contain many contaminants other than salts that make it unsuitable for various applications,
including drinking water. Such contaminants are typically many orders of magnitude larger
than the inorganic ions found in salts. When salt removal is not required, membranes with
larger pores would probably be sufficient for these applications. In addition to separation
applications, ordered macroporous (pore diameters 2–50 nm) or mesoporous (pore diameters
greater than 50 nm) materials could also find use in ion exchange [64], catalysis [65] and battery
technology [66]. A summary of the various pore sizes, including solutes that can be targeted in
this size range, examples in nature and their bioinspired equivalents is provided in figure 15
and table 1.
(a) Multicellular structures

A common method for the creation of biomimetic microporous membranes is through the use
of templating techniques. One early example is the use of bacterial threads to form ordered
Table 1. Examples of target solute, natural materials and bioinspired equivalents sorted by membrane pore size.
18
natural porous bioinspired porous

.........................................................
pore size target solute material material
macropores (>50 nm) bacteria (0.2–750 µm) eggshell, bacterial carbon nanotubes, templated silica
threads
...............................................................................................................................................................
oil emulsions (0.1–10 µm)

..........................................................................................................................................................................................................
mesopores (2–50 nm) colloidal solids surface layer proteins carbon nanotubes, self-assembled
(0.01–1 µm) block copolymers
...............................................................................................................................................................
viruses (20–400 nm)

...............................................................................................................................................................
proteins (2–10 nm)

..........................................................................................................................................................................................................
micropores (0.2–2 nm) inorganic ions aquaporins carbon nanotubes, amphiphilic

(0.2–0.4 nm) dipeptides, cyclic peptides,
crown ethers
...............................................................................................................................................................
water (0.2 nm)

..........................................................................................................................................................................................................
silica macrostructures. This was achieved by first slowly extracting a thread from a culture of
Bacillus subtilis, which caused the multicellular filaments to become aligned into a collection
of hexagonally close-packed cylinders [67]. The thread is then dipped into an aqueous sol
comprising colloidal silica nanoparticles. As the thread is dried, the nanoparticles coat the thread,
after which the organic material is then removed via heating to result in pore widths of 0.5 µm.
Other examples of templating membranes are shown in figure 16.
Template mineralization has been performed using the internal shell of Sepia officinalis or
cuttlefish (figure 16a) [68]. This cuttlebone consists of a highly organized structure comprising
calcium carbonate on a chitin framework. By removing the calcium carbonate from the
framework, the chitin can be remineralized using an aqueous sodium silicate solution. The chitin
template can then be removed by calcining. A similar technique used potato starch gels as the
template to create silicalite nanoparticle thin films with hierarchical porosity (figure 16b) [69]. It
was found that the pore size could be varied from 0.5 to 50 µm by altering the amount of starch
in the suspension.
Another method for creating template metal oxide membranes involved the use of eggshells
(figure 16c) [70]. Eggshells contain membranes with a macroporous network of interwoven fibres
with typical pore sizes of 5 µm. The membrane surface consists of amines and carboxylic acid
groups capable of interacting with titania precursors. The eggshell was first dipped in a tetra-
n-butyl titanium solution before being transferred to a propanol/water mixture, resulting in the
hydrolysis and condensation of titania onto the surfaces of the eggshell membrane. After removal
of the organic material through heating, a titania porous network remained. While the authors
theorized the material would have promising catalytic and photovoltaic properties, no studies of
the potential for these materials in separation techniques were carried out.
For smaller pore sizes, wood cellular structures have been combined with surfactant to create
hierarchically ordered porous material (figure 16d) [71,72]. The wood was soaked in a solution
containing surfactant and silicate. The silicate penetrated the cell walls and was hydrolysed
and condensed onto the internal structures of the wood. The surfactant was added and became
incorporated into the silica network, forming nanoporous channels necessary for the evacuation
of the organic matter during calcination. It was found that using different tree samples as the
template resulted in different pore diameter, volume and surface area. Pore sizes of 2.5–3 nm
were achieved. Despite several examples of biological materials being used as templates to create
(a) (b) 19

.........................................................
250 mm 50 mm
(c) (d)
5 mm 50 mm
Figure 16. Summary of various techniques for fabricating multicellular-inspired membranes: (a) cuttlebone-templated
silica featuring a highly organized internal structure (reproduced with permission from [68]. Copyright 2000 American
Chemical Society); (b) starch-templated silicalite where pore size is varied by altering the amount of starch (reproduced with
permission from [69]. Copyright 2002 American Chemical Society); (c) eggshell-templated titania featuring interwoven
fibres and typical pore sizes of 5 µm (reproduced with permission from [70]. Copyright 2002 John Wiley & Sons, Inc); and
(d) wood cellular-templated silica where changing the species of wood can alter the pore structure (reproduced with
permission from [71]. Copyright 2001 John Wiley & Sons, Inc.).
porous metal oxide films, these studies typically do not investigate the use of these materials in
the purification of water.
(b) Surface layer proteins

A collection of crystalline protein subunits called surface layers (S-layers) is a common structure
found on the surface of single-celled organisms. These S-layers contain pores typically 2–8 nm
in diameter. The specific size of the pores varies depending upon the species of organism they
reside upon. However, pore size is extremely uniform for a given S-layer, as it is determined by
the assembly of identical protein subunits [73].
S-layer-based membranes were prepared by suspending S-layer fragments in water and then
depositing them on a polymer support membrane with pore sizes of 0.1 µm [74]. The presence of
an intact S-layer membrane film covering the pores of the membrane support was confirmed
by size exclusion experiments, which displayed 100% rejection of the ferritin protein (12 nm
diameter). The existence of functional groups at well-defined positions and orientations within
the pores means that it is very straightforward to apply chemical modifications to the S-layer
membranes for improved selectivity and anti-fouling [75].
The creation and study of membranes comprising S-layer proteins is uncommon because of
instability and issues with scale-up. However, the technique of using the self-assembly of identical
subunits to form uniform-sized pores has been exploited when mimicking another pore-forming
protein, aquaporins.
(a) (b)
20
extracellular
a

c
.........................................................
c e
N194 I192, C191,
M2 G190, G189
M5 M7 conserved P195
M6 NPA motif
M8 ar/R
M4 A196
M3 M1 pore residues
H182
d
b R197 F58
C terminus
N terminus
cytoplasmic
Figure 17. Schematic showing (a) aquaporin in cell membrane and (b) top-down view of pore and surrounding amino acid
residues that contain hydrogen bond acceptors and donors to facilitate transport of water through the pore and act as selectivity
filters (Adapted with permission from [77]. Copyright 2014 Macmillan Publishers Ltd).
(c) Aquaporins
Aquaporins are pore-forming proteins found in living cells. Discovered in 1993 [76], for which
Peter Agre received the 2003 Nobel Prize in Chemistry, the proteins were found to facilitate a
rapid and selective transport of water while blocking the passage of ionic species. They do so
by folding in such a way that they form hourglass shapes, with a pore running down the centre
of each. At its narrowest point, the width of the pore is defined by a certain peptide sequence,
which allows different aquaporins to exhibit different pore sizes. Several clusters of amino acids
containing polar side chains create a hydrophilic surface and, as hydrogen bond acceptors and
donors, facilitate transport of water through the pore (figure 17) [77].
In some aquaporins, the small pore size (less than 0.3 nm) prevents passage of small molecules
and ions due to both steric and electrostatic effects [78]. Some aquaporins have been found to
allow the passage of small solutes—typically glycerol, urea and ammonia—and also cations,
though this topic remains controversial [79]. Other examples of aquaporins demonstrate various
forms of gating, where the channel may be open and closed via external stimuli [80]. Such
structures can be used to develop membranes with improved selectivity and permeability.
Aquaporin-based biomimetic membranes have therefore attracted a great deal of interest
due to their superior water flux and solute rejection when compared with conventional
membranes [81]. Typically, these membranes are fabricated by combining the aquaporin protein
(embedded within amphiphilic molecules, such as lipids) with a polymer support structure [82].
One early method for the creation of aquaporin biomimetic membranes involved the use
of laser ablation to create 300 µm holes in a poly(ethene-co-tetrafluoroethene) scaffold. A lipid
was then painted over the scaffold, forming a lipid bilayer film, which bridged the holes. The
aquaporin proteins were then introduced and became incorporated into the bilayer [83]. Such
lipid membranes are delicate and display very low lifetimes. Further support was given to
the scaffold by sandwiching it between two cross-linked hydrogels and building the whole
assembly on a cellulose membrane [84]. However, the lipid array lifetimes were still only several
days, and cross-linking of the hydrogel may compromise the functionality of the aquaporin
protein. Stability of the lipid membrane arrays was also improved by treating the scaffold
with plasma polymerization, leading to improved adhesion of the lipids to the substrate [85].
Lipid-embedded aquaporins have also been immobilized onto poly(ethylene oxide) (PEO)
hydrogel [86], PEO-coated porous alumina [87], mica [88], negatively charged silica [89], polymer-
coated silica [90] and nanofiltration membranes [91].
To overcome issues with the durability of lipid bilayers, researchers are instead using
amphiphilic block copolymers, which are more chemically and mechanically stable while also
(a) (b)
21

.........................................................
pore contains
R R
amino acid
side groups
R R
top-down view R R
R R
(c) (d)
OH
H H O
N N O HO OH
R
n R R
O O
O HO OH
O
HO OH
HO OH
R R
HO OH
OH
Figure 18. Summary of various techniques for fabricating aquaporin-inspired membranes: (a) cyclic peptides containing a
pore with a 0.7 nm internal diameter (adapted with permission from [93]. Copyright 1993 Macmillan Publishers Ltd);
(b) dendritic peptides featuring hydrophobic side groups within the pore for fast transport of water (adapted with permission
from [94]. Copyright 2007 American Chemical Society); (c) crown ethers where the size of the ring n can be altered; and
(d) cyclic arenes, which form hexamers that go on to form a channel with pores 1.8 nm in diameter.
allowing the incorporation of the aquaporin protein. One example of a polymeric membrane
containing the aquaporin protein was found to exhibit water permeabilities an order of
magnitude higher than conventional polymer membranes [92]. A remaining challenge is the
production of the aquaporins themselves. While aquaporins have been successfully produced
in a laboratory setting, it is typically in small quantities for characterization purposes, though
recent work suggests large-scale aquaporin production may yet be realized [61].
(i) Pore-forming molecules

In place of aquaporins, researchers have instead turned to other molecules that can mimic
the pore-forming nature of the proteins (figure 18). One example is the use of cyclic peptides
(figure 18a) [93]. The ring-shaped peptide consists of eight amino acids with alternating chirality
(D or L) such that all the amide functionalities lie perpendicular to the plane of the ring. This
allows for intermolecular hydrogen bonding between rings, resulting in a tubular structure that
was found to reach up to hundreds of nanometres in length. The alternating chirality also ensures
that the amino acid side groups (R groups) all lie on the outside of the ring structure to result in
tubes with an internal diameter of 0.7–0.8 nm. The authors suggested such structures could find
use in catalysis, electronics or separations; more recent studies have involved creating designs
more compatible with polymeric membrane processing [95].
Another example involves the use of dendritic (branched) dipeptides that can self-assemble,
either in solution or when cast in a film, into helical pores (figure 18b) [96]. Unlike the cyclic
peptides mentioned above, the pores formed from the dendritic dipeptides contain amino acid
22
side groups on their interior. This was found to result in a hydrophobic channel, which is
favourable for fast transport of water with high selectivity. It is also possible to alter the pore

.........................................................
structure by replacing sequences in the dipeptides. For instance, pore sizes can be varied from
0.2 to 2.4 nm by altering the peptide apex or branches. Proton transport measurements concluded
that these pores are functional.
Crown ethers are cyclic compounds consisting of multiple ether groups. In another example of
pore-forming molecules, crown ethers were functionalized with ureido groups (figure 18c) [97].
This molecule can self-organize into tubes via hydrogen bonding of these groups. By changing the
number of ether groups within the ring (n), the pore size can be altered. These molecular channels
were found to self-assemble within an existing lipid membrane, though conductivity studies of
species through the channels gave inconsistent results.

Finally, calixarenes are cyclic macromolecules featuring aromatic groups (figure 18d) [98].
These molecules were found to organize into nanotubes due to the interlocking of the side chains
(R groups), to form a cyclic hexamer featuring six molecules in a doughnut shape. It is these
hexamers that are then found to form the channel, with pore sizes of 1.8 nm. However, these
examples of pore-forming molecules are typically incorporated into lipid membranes and as such
their robustness is probably insufficient for commercialization.
(ii) Carbon nanotubes

Another approach to replicate the role of aquaporins with non-biological channels is with carbon
nanotubes (CNTs). CNTs are a cylindrical carbon-based material with atomically flat walls and
diameters ranging from 1 to 250 nm. Although they are intrinsically hydrophobic, water transport
has been found to be possible through such confined channels [99]. In fact, membranes containing
aligned CNTs have been found to exhibit water fluxes several orders of magnitude greater than
expected based on conventional models. It is theorized this could be because of the atomically flat
walls and the formation of hydrogen bonds between adjacent water molecules inside the tube,
both leading to a smooth energetic landscape for water travelling inside the nanotubes [100].
However, for nanotubes to act as purification membranes, either the nanotube diameter must be
small enough to reject solutes, or chemical modification must take place at the nanotube entrance
to increase selectivity [11].
CNTs have been successfully used as filters for the removal of contaminants of various sizes.
Aligned multi-walled carbon nanotubes (MWCNTs) were grown on a hollow carbon cylinder
through a spray pyrolysis technique. The inner diameter of the nanotubes was found to be 10–
12 nm. The material was found to remove Escherichia coli (2–5 µm), Staphylococcus aureus (1 µm)
and poliovirus (approx. 25 nm) from water [101]. However, smaller diameters are necessary for
blocking inorganic ions.
Narrower double-walled carbon nanotubes (DWCNTs) have been grown on a pitted silicon
chip via catalysed chemical vapour deposition and were encapsulated with vapour-deposited
silicon nitride (figure 19). Reactive ion etching was used to open the ends of the nanotubes, and
size exclusion measurements and transmission electron microscopy (TEM) images determined
the average inner diameter of the nanotubes to be 1.6 nm [102]. Despite the small pore size, the
DWCNT membranes were found to have superior permeability compared with conventional
polymer membranes. When negatively charged functionality is added to the entrance of the
DWCNTs, the membranes exhibit good ion rejection, a product of interactions between particle
charge and surface charge and not sterics [103]. However, aligned DWCNTs remain expensive to
fabricate.
(iii) Self-assembled block copolymers

Another analogue of aquaporins are self-assembled block copolymers. Manufacture of such
materials is more suited to scale-up when compared with CNTs and can be easily applied
(a) 1
(b) 23
CNTs
2

.........................................................
Si
3
10 mm
4
(c)
0.2
probability
5
0.1
6
0
0 1 2 3 4
7 inner diameter (nm)
Figure 19. (a) Schematic to show synthesis of aligned carbon nanotube membranes, (b) SEM image of carbon nanotubes atop
silicon substrate and (c) distribution of pore sizes as determined by TEM measurements. (Reproduced with permission from [102].
Copyright 2006 AAAS.)
to conventional porous supports. Self-assembly of block copolymers occurs due to inherent

differences between the constituent blocks, leading to phase separation. Selection of appropriate
conditions (concentration, solvent, drying times, etc.) can dictate this separation, to result
in various structures, including hexagonally packed cylindrical phases [104,105]. Selective
dissolution or etching of one of the blocks then results in a microporous structure comprising
the remaining polymeric material [104]. This technique is able to produce pore sizes of 8–30 nm.
Care must be taken when selecting the substrate and blocks in the copolymer. The substrate will
have an affinity for one block over another and this, along with surface roughness, will affect the
orientation of the polymer phases [106].
Phillip et al. [105] created membranes featuring 24 nm diameter, vertically aligned, hexagonally
close-packed pores by casting polystyrene-b-polylactide block copolymer and controlling the
solvent evaporation. The polylactide block was then selectively etched away using a base [105].
Water permeability was lower than expected, perhaps due to some pores not spanning the entire
depth of the PS layer. The authors predict a thickness of less than 100 nm is needed to ensure a
greater number of open-ended pores, though a polymer layer this thin will be difficult to achieve.
Another method to create porous polymer membranes is to add a separate sacrificial polymer
into the casting solution [107]. In one example, polystyrene-b-polyethylene oxide was blended
with polyacrylic acid and the solution was dip or spin coated onto various membrane supports,
achieving thin polymer layers of 200 nm. The sacrificial polyacrylic acid phase was removed by
soaking the polymer material in water overnight to leave open cylinders in the block copolymer
film [108].
Another method of creating porous polymer materials is to use a non-solvent-induced phase
separation process. In this technique, a concentrated diblock polymer solution is cast onto a
substrate. Solvent evaporation leads to microphase separation of the polymer blocks, similar to
the techniques described above. Before the film is completely dry, it is immersed into a non-
solvent, leading to exchange of the solvent with the non-solvent and a fixation of the structure.
This can lead to the formation of pores once the film is completely dry. This technique, therefore,
does not require the selective etching or dissolution of one of the polymer blocks.
A common example of this technique is polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP)
(figure 20) [109]. The diblock copolymer solution typically comprises a dimethylformamide
(DMF) and tetrahydrofuran (THF) solvent mixture. DMF is more selective towards P4VP, while
24

H2O
.........................................................
500 nm
Figure 20. (Top) Schematic of non-solvent-induced phase separation of polystyrene-b-poly(4-vinylpyridine) from THF/DMF
solvent mixture. Concentration-induced phase separation results in a less swollen PS matrix surrounding highly swollen P4VP
domains. Immersion in water results in solvent exchange within P4VP domains and solidification of water-insoluble PS matrix.
Eventual shrinking during drying of P4VP leads to formation of pores. (Bottom) SEM of porous block copolymer membrane.
(Adapted with permission from [109]. Copyright 2007 Macmillan Publishers Ltd.)
THF is more selective towards PS. The more volatile nature of THF leads to a concentration-
induced phase separation of the block copolymer, resulting in a less swollen PS matrix
surrounding highly swollen, cylindrical P4VP domains. Immersing the drying polymer film into
a non-solvent (in this case water) leads to solvent exchange in the swollen P4VP domains due
to water possessing a higher compatibility for P4VP than DMF. The water is guided through the
interconnected P4VP domains and leads to the solidification of the water-insoluble PS matrix. The
eventual shrinkage during drying of the swollen P4VP domains results in the formation of pores.
Size exclusion experiments determined the pores have an effective diameter of 8 nm, with an 82%
rejection of albumin.
By using a triblock copolymer, Mulvenna et al. [110] were able to produce nanoporous polymer
thin films with extremely narrow pore sizes via the non-solvent-induced phase separation
process. Moreover, they were also able to fabricate a porous material with easily tailored chemical
functionality on the pore walls [110]. The particular triblock copolymer was selected because of
the mechanical stability of the polyisoprene and PS domains, coupled with the ability to alter the
chemical functionality of the poly(N,N-dimethylacrylamide) (PDMA) domain. The use of water
as the non-solvent ensures that the pore walls are lined with the PDMA moiety, which can be
hydrolysed to poly(acrylic acid) (PAA). SEM images suggest a pore size of around 50 nm when
dried. However, effective pore diameters of 8 nm were calculated based on molecular weight cut-
off experiments (where the lowest-molecular-weight solute rejected by the membrane is used to
determine pore size). The discrepancy is attributed to the possible swelling of the PDMA domain
when wet. Conversion of the PDMA to PAA leads to a reduction in effective pore size to 3.4 nm
and pH-responsive permeability due to expansion of the PAA chains with increasing pH. Solutes
external
pressure H2O 25
Na+ Cl–

.........................................................
conventional
membrane
bioinspired
membrane
membrane
bioinspired
channel
external pressure is applied to overcome water molecules are able to pass through the
osmotic pressure and achieve reasonable water channels while ions are rejected due to steric
fluxes through low-permeability membrane and charge effects, resulting in higher
permeabilities and lower required pressures
Figure 21. Comparison of reverse osmosis membranes used in desalination. The semipermeable nature of the current
membranes results in the application of additional pressure to achieve reasonable water fluxes. Bioinspired membranes have
much higher permeabilities and require less applied pressure.
with radii above 1.25 nm were almost completely rejected [110]. Smaller pore sizes capable of ion
rejection have yet to be demonstrated.
(d) Outlook
Desalination via reverse osmosis is one of the more important purification techniques. However,
current membranes can have poor water permeabilities, requiring additional applied pressure
above that required to overcome osmotic pressure and achieve reasonable water fluxes
(figure 21).
Bioinspired membranes typically include a channel-forming component, such as carbon
nanotubes (figure 21). Current examples are typically found to exhibit higher permeabilities
compared with conventional membranes. For instance, even when added in very small
percentages, the incorporation of CNTs or aquaporins into commercial RO membranes results
in higher water flux and lower costs [11]. To be successful, these membranes must be highly
permeable, highly selective, mechanically robust and resistant to fouling.
However, there are some drawbacks to using CNTs for water purification. Creating aligned
single-walled CNTs and DWCNTs via chemical vapour deposition can be an expensive process
and not commercially feasible. MWCNTs are cheaper but cannot be used to create membranes
with small pore diameters. In addition, the CNTs must be further functionalized if they are
to display the ion rejection efficiencies necessary for desalination and these modifications
may alter or destroy the nanotube walls. For unmodified CNTs to display high ion rejection
efficiencies, even narrower pore diameters than currently demonstrated will be required [100].
Molecular dynamics simulations suggest that CNTs with inner diameters of 0.5 nm are capable
of achieving a 95% salt rejection [100], adequate enough to convert seawater into water fit for
human consumption, but still lagging behind commercial RO membranes, which boast 99.7% salt
rejection [111]. CNT membranes with sub-nanometre pore diameters have yet to be fabricated.
Another system capable of pore formation is self-assembled block copolymers. However,
though they offer advantages over CNTs, such as ease of fabrication, there are also some
drawbacks. Currently, the pore size achievable through this method is still quite large, with pores
<2 nm yet to be fabricated. Although pore size distribution is typically very narrow, resulting in
high selectivity, the large pore diameters preclude these membranes from certain applications,
such as desalination, unless some mechanism for solute rejection is added to the membrane via
chemical modification of the pore entrance or walls [110]. In addition, fouling and pore blockage
remain an issue because of the surface properties of many of the polymers used and so further
26
surface modification is necessary [112].

.........................................................
4. Separating water from oil
The Deepwater Horizon oil spill in 2010 was the largest accidental offshore oil spill in history,
with 206 million US gallons of oil being released into the Gulf of Mexico (table 2) [114]. In
addition, the emergence of fracking in the United States, where water-based fluids (containing
sand and chemicals) are injected under high pressure to fracture rocks for the release of previously
inaccessible oil and gas, has led to a large increase in domestic oil production (figure 22). However,
the process has also led to an increase in the amount of oil-contaminated wastewater. It is
estimated that, between 2005 and 2014, 248 billion US gallons of water were used for shale gas
and oil extraction in the United States [117]. In addition to this large amount of wastewater
that must be processed before release, there is the potential for accidental contamination of
ground and surface water. In 2013, the state of Pennsylvania received nearly 400 complaints
about private water wells being affected by oil or gas drilling [118]. Remediation of oil spills
and separation of oil from water is therefore an important environmental challenge. While the
purification membranes described above are capable of removing the chemical contaminants
resulting from fracking, where the amount of contaminating oil is relatively low, their low water
flux and tendency to suffer from surface fouling can make them unsuitable for clean-up of larger
oil spills.
One common method currently used for oil-spill remediation is the use of dispersants,
chemicals that reduce the interfacial tension between oil and water to facilitate break-up of the
oil into smaller droplets. However, the toxicity and poor biodegradability of both dispersants and
the resulting dispersed oil makes using such chemicals a controversial choice [119]. Skimming of
the oil from the surface of the water with absorbent booms is one method of removal; however,
this is dependent upon favourable conditions including calm waters and slow oil speeds.
Other methods for the collection of the oil use other absorbent materials such as zeolites [120],
organoclays [121] or natural fibres [122] such as straw [123], cellulose [124], wool [125] or human
hair [126]. However, many of these materials have a tendency also to absorb water, which can
lower their efficiency [127]. Additionally, the absorbed oil must be removed from the material,
making such methods incompatible with continuous-flow systems.
Separation filters and membranes that repel one liquid phase while allowing the other to pass
through also exist. Unlike the porous materials detailed above, these are commonly designed for
maximum permeation, at the cost of some degree of selectivity.
In nature, extreme liquid repellency is evident in the lotus leaf [9,12,13,128]. Lotus leaves are
found in muddy ponds, and yet the leaf surface is typically clean. Water droplets falling on the
leaf are found to exhibit high contact angles and a low hysteresis due to being in the Cassie–Baxter
state of wetting (see appendix A). Therefore, they move easily across the leaf, collecting debris as
they go and keeping the leaf clean for photosynthesis (figure 23a). The superhydrophobic nature
of the leaf surface is a result of its chemistry and topography. It is composed of a hierarchical
structure of micropapillae and nanotubules. The nanotubules are made of a hydrophobic wax
and, when combined with the micropapillae, result in a superhydrophobic surface [128,130].
Oils have a much lower surface tension than water [131]. It is therefore possible to design
surfaces that repel water but have an affinity for oils. Inspiration can be taken from the lotus leaf
to create hierarchically structured surfaces. The hierarchical roughness will enhance the chemistry
of the surface, resulting in high water contact angles and low oil contact angles, ensuring good
separation can be achieved when the treatment is applied to a porous substrate.
An early example utilized a polytetrafluoroethylene (PTFE) emulsion, which was spray coated
onto steel meshes with various pore diameters (figure 24) [132]. The resulting coated mesh was
superhydrophobic and superoleophilic, with contact angles of 150◦ and 0◦ for water and diesel
oil, respectively. When oil was added to the mesh, it quickly spread and permeated the mesh to
be collected on the other side, while water added to the mesh remained on top.
450
fracking 27
million US gallons a day

400 becomes
350 viable

.........................................................
300
250
200
data from [116]
150
1985 1990 1995 2000 2005 2010 2015
year
well flowback water leaks

well leaks
water table fracture zone leaks
fissures
shale high-pressure fracturing fluid

flowback
water
with oil
and gas
Figure 22. Schematic of the fracking process. High-pressure fluid (typically water, sand and chemicals) is pumped underground,
creating fissures and releasing previously inaccessible pockets of oil and gas, which are then removed along with the fluid.
Leaks of contaminated fracking fluid into groundwater are possible from the fracture zone, the well and flowback water storage
containers. Inset: US crude oil production. Increase in production from 2010 is due to the emergence of fracking, primarily
occurring onshore in the lower 48 states.
Table 2. List of notable offshore oil spills.
amount spilled
spill location year (million US gallons)
b
Deepwater Horizon Gulf of Mexico 2010 206
..........................................................................................................................................................................................................
a
Gulf War Persian Gulf 1991 240
..........................................................................................................................................................................................................
ABT Summerc Angola 1991 80

..........................................................................................................................................................................................................
c
MT Haven Italy 1991 42
..........................................................................................................................................................................................................
c
Valdez Alaska 1989 11
..........................................................................................................................................................................................................
c
Odyssey Canada 1988 43
..........................................................................................................................................................................................................
a
Nowruz Persian Gulf 1983 80
..........................................................................................................................................................................................................
c
Castillo de Bellver South Africa 1983 79
..........................................................................................................................................................................................................
a
Ixtoc I Gulf of Mexico 1979 140
..........................................................................................................................................................................................................
c
Atlantic Empress West Indies 1979 88
..........................................................................................................................................................................................................
Amoco Cadizc France 1978 69

..........................................................................................................................................................................................................
a From [113].
b From [114].
c From [115].
(a) (b) water droplets lotus leaf 28
air

.........................................................
water oil droplets
Figure 23. (a) A water droplet on the top surface of a lotus leaf exhibiting high contact angles and (b) droplets of oil under
water exhibiting high contact angles when placed on the underside of the leaf. (Adapted from [129]. Copyright 2011 The
Royal Society of Chemistry.)
water
diesel oil
100 mm
Figure 24. Superhydrophobic/superoleophilic mesh created using a spray-coated PTFE emulsion. Droplets of water remain on
the topside of the mesh while oil droplets soak through. (Reproduced with permission from [132]. Copyright 2004 John Wiley
& Sons, Inc.)
In another example, filter paper was dip coated into a mixture of hydrophobic nanoparticles
and polymer binder [133]. The resulting hierarchical roughness causes high water contact angles
of 157◦ and low oil contact angles, with oil observed to quickly wick into the filter paper. When an
oil–water mixture is poured onto the filter paper, the oil passes through while the water remained
on the surface and could be rolled off.
However, in such configurations where the surface is oleophilic, surface contamination by
oil and other oil-based contaminants is common, and the porous material must be cleaned or
replaced, resulting in a drop in the separation efficiency. Additionally, water is denser than oil
and tends to sink to the bottom of a mixture, meaning hydrophobic/oleophilic materials are not
suitable for certain applications, such as gravity-driven separation.
An alternative method that once again is inspired by the lotus leaf, and other natural surfaces,
is to use a surface that is oil repellent when under water. Examples of oil repellency in nature
are generally limited to underwater oil repellency; for example, shark skin is oleophilic in air but
superoleophobic under water [134]. This is due to a hydrophilic coating that would rather interact
with water than oil. As mentioned above, the top of the lotus leaf is superhydrophobic due to wax
nanotubules. However, the underside of the leaf has no such structures and is hydrophilic. When
floating on water, the underside of the leaf is, therefore, superoleophobic (figure 23b) [129].
Underwater superoleophobic surfaces have been created by immersing steel mesh into an
acrylamide solution. The acrylamide was polymerized by UV irradiation to form a hydrogel, a
water-swollen polymer network [135]. When placed under water, the treated mesh exhibited oil
water water 29
oil oil

.........................................................
substrate substrate
oil
coated
mesh
water
Figure 25. Underwater superoleophobic mesh created using a hydrogel coating. Oil droplets roll from the mesh when placed
under water. (Reproduced with permission from [135]. Copyright 2011 John Wiley & Sons, Inc.)
contact angles of 153◦ and droplets were found to roll easily from a tilted surface. When an oil–
water mixture was poured onto the mesh, the water permeated through the mesh while the oil
remained on top (figure 25). Although this configuration helps reduce the impact of fouling, the
fact that the surface is only superoleophobic under water limits its application.
Surfaces that are superoleophobic in air are typically also superhydrophobic due to water
having a higher surface tension. Such surfaces would, therefore, be unsuitable for oil–water
separation as the interactions with both liquids are similar.
However, it is possible to create a coating that repels oils but has an affinity for water [136–
141]. This is achieved through the use of a fluorosurfactant, which contains a high-surface-energy
head group and a low-surface-energy tail group. Fluorosurfactants are typically used as additives
in paints or cleaners. However, the presence of the ionic head group in many examples allows
for complexation, either in solution or on a coating, with polyelectrolytes. After deposition, the
fluorinated tails segregate at the air interface, resulting in a low-surface-energy barrier that repels
oils. However, when droplets of water are placed on the surface, they are able to penetrate down
through the tail groups to reach the high-surface-energy groups below [142]. The coating therefore
appears hydrophilic while also being oleophobic. However, many examples of these surfaces have
several drawbacks, including poor oleophobicity [143–145] or poor water penetration, resulting
in a coating that is initially hydrophobic [139,145–148].
Brown & Bhushan [141] have created a superhydrophilic/superoleophobic surface by
combining the chemistry of the fluorosurfactant with hierarchical roughness inspired by the lotus
leaf [141] (figure 26). The fluorosurfactant provides oil repellency and water affinity, while the
roughness enhances these properties to result in oil contact angles of greater than 150◦ and water
contact angles of less than 5◦ . When this coating is applied to a steel mesh and an oil–water
mixture is poured over it, the water penetrates through the mesh while the oil remains on top
and can be easily rolled off by tilting. By inclining the mesh at an angle, the two liquids can be
separated and collected simultaneously.
Such surfaces represent the ideal scenario for oil/water separators. Their oil-repellent nature
means they are less prone to fouling than devices where the water phase is being repelled.
In addition, their water affinity makes them more compatible with gravity-driven separation,
where the water phase will be at the bottom of the mixture, or in scenarios where water is the
dominant phase. The use of nanoparticles enhances the oil repellency and water affinity, ensuring
good separation efficiencies as well as quick penetration by the water phase. The nanoparticles
(a) fluorosurfactant layer (FL)
– 30
+ PDDA binder (2)
– SiO2 nanoparticles
+

.........................................................
PDDA binder (1)
– glass
(b) flat PDDA/FL layer-by-layer

composite
100 1
nm mm
–100 –1
0 100 mm 0 100 mm
0 nm 100 nm 0 mm 1 mm
(c)
oil/water
mixture
water oil
Figure 26. Superoleophobic/superhydrophilic mesh created using spray-coated layer-by-layer technique. (a) Coating
comprises fluorosurfactant layer for oil repellency and water affinity, SiO2 nanoparticle layer to enhance surface properties and
increased durability, and binder layers for adhesion. (b) AFM wear experiments (one cycle at 10 µN) demonstrate increased
durability of layer-by-layer coating compared with flat coating. (c) Oil–water separation ability of coated mesh [141].
also increase the hardness, resulting in a coating that is much more durable than previous
examples [141,149].
Importantly, unlike absorbent materials, both phases are immediately separated, with no
additional steps required to remove one phase from the material. It is envisioned that such a
device could be used upstream of the conventional purification membranes detailed above. This
ensures that the majority of the contaminant phase is removed before further purification and
processing, resulting in greater efficiency of the more selective membranes.
(a) Outlook
Despite advances in other energy sources, with a global population reaching 8.2 billion by
2030 [4], oil and gas will continue to play an important role in meeting rising energy demand.
absorbent boom bioinspired nets 31
bioinspired
coated
net

.........................................................
oil-free
water
oil
absorbent
boom
Booms require favourable conditions, including Nets featuring bioinspired coated mesh trap
calm waters and slow oil speeds. Oil can oils while allowing passage of water. Oil can
easily slip under or be washed over the easily be recovered from nets via pumping.
boom. Extra steps required to extract oil from Oil-repellent nature of mesh reduces need
booms. Booms require regular cleaning or for cleaning.
replacement.
Figure 27. Comparison of absorbent booms commonly used during oil-spill remediation and bioinspired nets. The booms
absorb the oil from the surface of the water but require favourable conditions and must be regularly cleaned to recover the
oil. The bioinspired nets will capture the oil, where it can be recovered by pumping, while allowing water to pass through.
(Online version in colour.)
This, combined with the increase in fracking, makes future oil spills and contamination of water
increasingly likely.
One current method for remediation of oil spills consists of absorbent booms that require
favourable conditions and must be cleaned before the oil can be recovered (figure 27). Combining
hierarchical roughness, inspired by the lotus leaf, with chemistries not available to nature
has resulted in materials that can separate oil from water. Specially coated nets could aid
oil-spill clean-up by trapping the oil in the net while allowing the water to pass through
(figure 27). Future challenges include improving the selectivity of these devices to achieve higher
separation efficiencies, without compromising the permeabilities that set these materials apart
from traditional purification membranes. Such materials are also of relevance in a wide range
of applications, including treatment of wastewater from the metal, textile or food processing
industries, and for scenarios where contaminant water must be removed from oil, for instance
in engine components.
5. Concluding remarks
Water is the key to all life. It was the medium into which life itself began. It is vital for not just our
survival, but also the survival of all living things on the planet. Over some 3 billion years, various
species have evolved ingenious ways to collect and transport this vital fluid. From the hydrophilic
spots on a beetle’s back, to the tiny proteins lining our cells, their size and complexity may vary
but their purpose remains the same: to get water to where it is needed. By taking inspiration from
nature’s ingenuity, it is hoped we can solve our own water crisis through the creation of materials
for water collection, water purification and separation of water from oil (figure 28).
When looking to nature, one thing that is immediately clear is its abundance. Nature is able to
thrive in the harshest environments, including some of the driest places on the Earth. One way it
does this is by using alternative sources of water, such as fog. By studying these examples, from
beetles to cacti, it is hoped that new materials can be developed to help improve the efficiency of
existing fog-harvesting strategies and further establish the technique as a viable source of water
for communities all over the world.
32
contaminated water contaminants

.........................................................
pur
n
tio
clean water
ific
membrane
lec
water molecules
atio
col
n
collected water
fog
water
collec
tor bioinspired materials
for water supply and
management
collected oil
oil-free water
oil-spill
separation from oil
Figure 28. Bioinspired materials for water supply and management: collection, purification and separation from oil.
Purification of salt water, from the oceans or brackish groundwater, could also provide
an abundant source of water for many regions. However, the process of desalination is
energy-intensive. Nature has evolved efficient pathways in our own body to facilitate the
transport of water while blocking other species. It is hoped that, by taking inspiration from
the chemistries and structures of these natural channels, artificial ones can be created that can
improve not just desalination efforts, but also purification of other water sources that too easily
become contaminated, often by human activities.
In that vein, contamination of water by oil is a problem that has plagued human progress in
the last few centuries. This relatively new resource is constantly threatening sources of water,
and while it is always hoped that large-scale oil spills are a thing of the past, disasters such as
Deepwater Horizon show us that, so long as oil is sought, the danger will be there. Once again,
we can learn from nature and, by studying how natural surfaces interact with liquids, can develop
new techniques for cleaning up the mess that we, regrettably, continue to make.
Water is a human right [1]. However, it is a right that is currently under threat for many
people across the world, including some in the United States, one of the most developed and
economically stable countries in the world. It is hoped that nature can provide us with the tools
we need to help restore this right to all people.
Competing interests. We declare we have no competing interests.
Funding. We received no funding for this study.
Acknowledgements. Many thanks to Dev Gurera for creating several figures for this review and to Renée Ripley
for creating figures and providing helpful suggestions and corrections.
(a) glv vapour 33

.........................................................
liquid
q
gsv gls solid
(b) (c)
complete air
wetting pockets
Wenzel state Cassie–Baxter state

(d) (e)
qrec
original
position qrec
qadv
qadv
high hysteresis low hysteresis
Figure 29. (a) Liquid droplet displaying contact angle of θ on flat surface, (b) droplet exhibiting Wenzel state of wetting,
(c) trapped air between droplet and surface in Cassie–Baxter state of wetting, (d) droplet exhibiting high contact angle
hysteresis and (e) droplet exhibiting low contact angle hysteresis. (Online version in colour.)
Appendix A. Background on surface wettability

The ability to control liquid droplets is made possible by altering how they interact with the
surface upon which they are resting. A droplet of water on a solid surface forms a spherical
shape, which is determined by a combination of interfacial tensions,
γsv − γsl
cos θ = , (A 1)
γlv
where γsv , γsl and γlv are the solid–vapour, solid–liquid and liquid–vapour surface tensions,
respectively, and θ is the contact angle of the resulting droplet (figure 29a). Water contact angles
<90◦ result in a surface that is considered hydrophilic (water loving), whereas surfaces exhibiting
angles >90◦ are hydrophobic (water fearing) [9].
When a surface is roughened, contact angles change due to amplification of the solid–liquid
interactions; hydrophilic surfaces become more hydrophilic and hydrophobic surfaces more
hydrophobic (figure 29b) [150]. It is also possible for air pockets to become trapped between the
solid and the liquid, resulting in a composite interface and, as the liquid is resting partially on air,
a more repellent surface (figure 29c) [151].
However, a rough surface can exhibit contact angle hysteresis. This is where the contact angles
of a mobile drop are different for the leading edge and the trailing edge (figure 29d). As the leading
edge of a droplet moves, it does so with a certain contact angle known as the advancing contact
angle (θadv ). When the trailing edge begins to move, it will do so with a receding contact angle
(θrec ). The advancing and receding edges may have different respective contact angles; this is the
contact angle hysteresis. Typically, a low hysteresis is preferred to ensure the water droplets roll
over the surface easily (figure 29e) [9].
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Bioinspired materials for water

supply and management:

Bioinspired materials for water supply and

Accepted: 21 April 2016 Access to a safe supply of water is a human right.

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

condensing water vapour

evaporation surface run-off

ocean channel run-off

water consumption (1012 m3 yr–1)

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

1 Oceania Africa Americas

projected data from [5]

Figure 2. Actual (1980–2010) and projected (2030) global water consumption.

no water stress low water stress

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

(a) Namib Desert beetles

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

Stenocara gracilipes (beetle)

action directs water through

asymmetric channels, favouring

Moloch horridus (lizard)

knot due to Laplace pressure and

Araneae (spider web)

water droplets are channelled

towards the base of the plant

water droplets grow on tiny

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

silica aerogel copper block

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

(c) Spider webs

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

spindle knot joint

(c) stretched porous structure (d) random porous structure

(e) t = 7.708 s ( f ) t = 7.955 s (g) t = 8.116 s

t = 8.427 s t = 8.588 s t = 8.717 s

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

(e) Other plant species

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

polymer net bioinspired net

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

water moves through semi- external pressure is applied to

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

material layer threads

(a) Multicellular structures

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

oil emulsions (0.1–10 µm)

viruses (20–400 nm)

proteins (2–10 nm)

micropores (0.2–2 nm) inorganic ions aquaporins carbon nanotubes, amphiphilic

water (0.2 nm)

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

(b) Surface layer proteins

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

(i) Pore-forming molecules

rsta.royalsocietypublishing.org Phil. Trans. R. Soc. A 374: 20160135

species through the channels gave inconsistent results.

(ii) Carbon nanotubes