Articles

https://doi.org/10.1038/s41565-018-0097-z

Highly efficient solar vapour generation via

hierarchically nanostructured gels
Fei Zhao1,4, Xingyi Zhou1,4, Ye Shi1, Xin Qian2, Megan Alexander1, Xinpeng Zhao2, Samantha Mendez1,
Ronggui Yang2*, Liangti Qu3* and Guihua Yu1*

Solar vapour generation is an efficient way of harvesting solar energy for the purification of polluted or saline water. However,
water evaporation suffers from either inefficient utilization of solar energy or relies on complex and expensive light-concen-
tration accessories. Here, we demonstrate a hierarchically nanostructured gel (HNG) based on polyvinyl alcohol (PVA) and
polypyrrole (PPy) that serves as an independent solar vapour generator. The converted energy can be utilized in situ to power
the vaporization of water contained in the molecular meshes of the PVA network, where water evaporation is facilitated by the
skeleton of the hydrogel. A floating HNG sample evaporated water with a record high rate of 3.2 kg m−2 h−1 via 94% solar energy
from 1 sun irradiation, and 18–23 litres of water per square metre of HNG was delivered daily when purifying brine water. These
values were achievable due to the reduced latent heat of water evaporation in the molecular mesh under natural sunlight.

S
olar energy is a promising source for boosting the evolution of
renewable energy technology. Despite the unmatched resource
potential of solar energy, the restricted utilization efficiency
presents an enormous challenge1–3. Solar-to-thermal technologies,
such as domestic heating4, brine desalination5–8 and power gen-
eration9–11, have been the subject of both academic research and
industrialization efforts throughout the past decades. Solar vapour
generation that can directly transfer heat to facilitate evaporation
is an efficient way to harvest solar energy and to purify water12.
As solar radiation serves as the only power input for vapour gen-
eration, a variety of materials, including ultra-black absorbers13–16,
plasmonic nanoparticles17–20 and thermal-concentrating ceramics21,
have been used to enhance the conversion efficiency. However, the
inefficient utilization of converted heat imposes an additional chal-
lenge. Among the three major heat consumption processes, that is,
water heating, parasitic thermal loss and water vaporization, only
water vaporization is effective8. Therefore, adequate thermal man-
agement in the solar vapour generation system is essential. The heat
localization strategy, which restricts heat into a small amount of
water in the evaporating surface, may substantially improve the effi-
ciency of solar energy utilization22–24. Though it has been demon-
strated that efficiency can be increased by using concentrated solar
power with high flux values (10 kW m−2 or higher)19,25–27, it would be
ideal to achieve highly efficient solar vapour generation under 1 sun
(1 kW m−2) or even weaker natural daylight.
Here, we report an efficient in situ energy utilization strategy
based on HNGs to achieve high energy conversion efficiency and,
more importantly, high water evaporation rates under 1 sun. We
present an energy confinement strategy based on water manage-
ment through hierarchical water pathways in a hydrogel28, which
consists of internal gaps, micron channels and molecular meshes
(Fig. 1a). Furthermore, the water in the molecular meshes of HNGs
have a reduced vaporization enthalpy29. To accomplish solar evapo-
ration, a floating HNG is exposed to solar irradiation (Fig. 1b). Due
to the penetration of solar absorbers (PPy) in the polymeric gel PVA
network, the converted solar energy can be directly delivered to the
small amount of water in the molecular meshes (see 1 in Fig. 1b).
PVA chains eradicate the convective heat loss of water30,31, which is
conventionally the main energy loss channel in solar vapour gen-
erators with thermal localization effects. Additionally, the rapid
water diffusion and capillary pumping of micron channels (see 2 in
Fig. 1b) and internal gaps (see 3 in Fig. 1b) lead to rapid replenish-
ment of the molecular meshes through swelling of the polymeric
network to support a sustained high rate vapour generation. A high
water evaporation rate of 3.2 kg m−2 h−1, almost two times higher
than the reported record19, was achieved under 1 sun solar radia-
tion with excellent stability and durability. Furthermore, the HNG
exhibited a daily solar water purification yield of 20.3 l m−2 under
natural sunlight, indicating its potential for scalable manufacturing
for practical applications in the future.
Fabrication and characterization of the HNGs
We used the in situ polymerization method for preparing the inter-
penetrating structured HNGs30 (see Supplementary Methods for
details). As PVA plays the role of surfactant to assist the dispersion
of PPy in water, the basic building block (precursor) of HNG was a
PVA–PPy cluster (Supplementary Fig. 1). After gelation, the spac-
ing among these clusters formed the internal gaps and the clusters
formed the skeleton of the HNG with micron channels. The as-pre-
pared HNGs were black (Fig. 2a), flexible and elastic (Supplementary
Fig. 2). Scanning electron microscopy (SEM) showed that the HGNs
exhibited broad gaps with diameters of ~150 μ​m (highlighted by the
red broken line in Fig. 2b) that segmented the porous structure. The
pores formed micron channels that had widths ranging from several
microns to tens of microns (Fig. 2c). In addition, the wall structure
showed a wrinkled internal surface (Fig. 2d), indicating shrinkage
of the polymeric skeleton (PVA network) during dehydration of the
hydrogel (Supplementary Fig. 3). Combined with the nanostruc-
tures, a three-dimensional (3D) hierarchical network of water path-
ways, such as arteries and branches, was established in the HNGs.

1
Materials Science and Engineering Program and Department of Mechanical Engineering, The University of Texas at Austin, Austin, TX, USA.
2
Department of Mechanical Engineering, University of Colorado, Boulder, CO, USA. 3Key Laboratory of Photoelectronic/Eletrophotonic Conversion
Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, China. 4These authors contributed equally:
F. Zhao, X. Zhou. *e-mail: ronggui.yang@colorado.edu; lqu@bit.edu.cn; ghyu@austin.utexas.edu

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Articles
a Water and energy management in the HNGs
Internal gap Micron channel Molecular mesh
PVA PPy Crosslinking point
b generation, the saturated water content (denoted as Qs; Fig. 3a) and
Water transport
Confined
Solar evaporation
radiation 1
Bran
ch
2 diffus ed
ion
3
HNG Ar
pu teria
mp l
ing
Bulk wat
er
Fig. 1 | Schematic of highly efficient solar vapour generation based on
tailored water transport in HNGs. a, The HNG consists of hierarchical
porous structures, including internal gaps, micron channels and molecular
meshes, wherein the solar absorber (PPy) penetrates the polymeric PVA
network of the gel. b, Schematic of a typical solar vapour generation
system and the water confinement strategy. Under solar radiation, the
solar absorbers in the molecular meshes of the floating generator are
heated, facilitating the evaporation of water confined in the polymeric
network (1). The water confined in the molecular mesh has a reduced
evaporation enthalpy. The evaporated water can be rapidly recovered via
branched water diffusion (2) and pumping (3) based on micron channels
and internal gaps, respectively.
As polymeric hydrogels are viscoelastic materials, the additive
penetrating the skeleton alters energy storage and energy dissipa-
tion, which can be represented by the storage modulus (G′​) and
the loss modulus (G″​), respectively32. The G′​and G″​values of a
HNG and a pure PVA gel are shown in Fig. 2e. The dynamic fre-
quency sweep experiments of both gels show a wide linear visco-
elastic region. The G′​value is higher than the G″​value in each
case, confirming their crosslinked polymeric skeleton. The lower
G′​value of the HNG indicates that it has fewer crosslinking points
than the PVA gel, while the lower G″​value of the HNG reveals
an efficient restriction of the slippage between polymer chains33
(discussed in detail in Supplementary Fig. 4). These results dem-
onstrated that the PPy chains were inserted into the molecular
meshes of the PVA network, indicating that the solar absorber was
selectively introduced into the HNG-confined water (that is, only
in the molecular meshes).
The chemical composition of the HNGs was analysed by
Fourier transform infrared (FTIR) spectroscopy. In the PVA spec-
trum (red curve in Fig. 2f), the peaks located at 1,093 cm−1 can
be attributed to C–O stretching, which is a characteristic peak of
PVA34. The PPy spectrum (blue curve in Fig. 2f) shows absorp-
tion signals at 1,552 cm−1 and 1,045 cm−1, corresponding to the
in-ring stretching of C=​C bonds in the pyrrole rings and the in-
plane deformation of N–H bonds, respectively35. All the charac-
teristic peaks of PVA and PPy were found in the FTIR spectra of
HNG (black curve in Fig. 2f) without shifts, thus confirm-
ing the presence of PPy in the PVA matrix. These results were
in good agreement with the thermogravimetric analysis data
(Supplementary Fig. 5).
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Nature Nanotechnology
The weight ratio between water and PVA was tuned to
control the nanostructure32,36 and hence regulate the
water content and transport in the HNGs with the opti-
mized PPy/PVA ratio of 1:10 (Supplementary Figs. 6–8).
HNGs with water/PVA weight ratios of 1:0.2, 1:0.15, 1:0.1 and 1:0.075
were prepared (designated as HNG1, HNG2, HNG3 and HNG4,
respectively) to evaluate structure-dependent water transport.
Given that the HNGs were completely hydrated during solar vapour
the half swollen time (blue curve in Fig. 3a; see Supplementary Fig.
9 for more details) of different HNG samples were measured to cal-
culate the water transport rate (denoted as V; red curve in Fig. 3b).
The results confirmed that the Qs and V were affected by the nano-
structured channels (Supplementary Figs. 10 and 11).
As shown by the ultraviolet–vis (UV–vis) near infrared (NIR)
spectra in Fig. 3c, the HNGs presented excellent absorption fea-
tures throughout the solar spectra with negligible optical loss. In
addition, the HNGs showed low reflectance over a wide wave-
length range (from 250 to 2,000 nm) (Supplementary Fig. 12a).
Consequently, the light absorption of the HNGs is not sensitive to
the Qs or V values, enabling stable solar energy harvesting during
vapour generation. In addition, a ~400-μ​m-thick HNG sheet pro-
vided an average transparency of ~2% (Supplementary Fig. 12b),
indicating that the thickness of the effective solar energy harvesting
region in HNGs is ~400 μ​m. Moreover, the Qs and V values were
independent of the thickness (Supplementary Fig. 13). Despite the
identical energy harvesting ability of different HNGs, the utiliza-
tion of solar energy for water heating and evaporation depended
strongly on the Qs and V values. Within 500 s, the surface of HNG1,
HNG2 and HNG3 could be heated to an equilibrium temperature
(Fig. 3d). The different linear dependence between the surface
temperature and time represented a different energy consumption
method. The sharply increasing region indicated that the heat was
mainly utilized to raise the temperature, while the plateau region
indicated the tremendous energy consumption of evaporation
(known to be associated with the cooling effect). As the evaporation
of water is accelerated with increasing temperature, the inflection
point showed an energy balance value of water heating and evapo-
ration. The low equilibrium temperature indicated the optimum Qs
and V values for solar vapour generation. Accordingly, as the Qs and
V values increased further, the surface temperature of HNG4 rose
gradually and continued increasing after exposure to solar radia-
tion for 2,500 s; therefore, the converted energy was used to heat the
water instead of powering evaporation. The corresponding HNG1
to HNG4 xerogels could be identically heated to ~90 °C in a short
period of time (Supplementary Fig. 14).
Solar vapour generation under 1 sun
Under constant solar illumination (1  kW  m−2), the overall
mass change with and without HNGs, which represented the
amount of evaporated water, was recorded once the tempera-
ture reached steady state (pre-heating for ~500 s, see above).
It is clear that vapour generation with the HNGs is more effi-
cient than pure water without HNG under 1  sun radiation
(Fig. 4a). HNG3 presented an extremely high rate of 3.2 kg m−2 h−1,
which was 1.3, 2.5 and 8 times that for HNG2, HNG1 and pure
water (shown by red squares in Fig. 4b), respectively. However,
HNG4, which presented an even larger water content in the molec-
ular meshes, showed a low rate of 0.7 kg m−2 h−1. These results
revealed that HNG3 has an optimized water content. Additionally,
the control experiments conducted under concentrated solar illu-
mination also demonstrated that HNG3 presented the best per-
formance (Supplementary Fig. 15). Note that all the experimental
data of solar vapour generation are calibrated to dark-condition
evaporation data (see Supplementary Methods for details), and the
Nature Nanotechnology Articles
a b e
106 106
PVA gel
10 5
HNG 105
10 4
104

G′ (Pa)

G′′ (Pa)
103 103
10 2
102
Internal 10 1
101
gap 100 100
1 cm 100 μm 1 10 100
Frequency (rad s–1)
c d f

Transmittance (a.u.)
HNG

PPy
Micron
channel PVA

4,000 3,000 2,000 1,000

5 μm 1 μm
Wavenumber (cm–1)

Fig. 2 | Characterization of the HNGs. a, Photograph of an as-prepared HNG. b–d, SEM images of HNGs at different magnifications showing internal
gaps (b), micron channels (c) and the wrinkled internal surface (d); the wrinkled internal surface indicates shrinkage of the polymeric skeleton during
dehydration. e, Dynamic mechanical analysis of the storage modulus (G′​) and loss modulus (G″​). The results demonstrate that PPy penetrates the
molecular meshes among the PVA network. f, FTIR spectra of a HNG, PVA and PPy showing the chemical composition of the HNGs.

a b
42
8 0.12
Half swollen time (min)

39
Saturated water

Water transport
content (g g–1)

rate (g min–1)
6
36 0.08

4
33
0.04
2 30

27 0.00
HNG1 HNG2 HNG3 HNG4 HNG1 HNG2 HNG3 HNG4
c d 50
100 1 sun

HNG1
Temperature (°C)
Absorption (%)

HNG2 40
HNG3 HNG1
90 HNG4 HNG2
AM 1.5 G HNG3
30
HNG4

80 20
500 1,000 1,500 2,000 2,500 0 500 1,000 1,500 2,000 2,500
Wavelength (nm) Time (s)

Fig. 3 | Tunable water transport and solar absorption of the HNGs. a, Saturated water content in HNGs per gram of corresponding xerogel samples. Each
error bar represents the deviation from at least 15 data points. b, Swollen behaviour from the half-saturated to the saturated state and the calculated water
transport rate showing the tunable water transport ability of the HNGs. HNG1, HNG2, HNG3 and HNG4 represent gels with water/PVA weight ratios of
1:0.2, 1:0.15, 1:0.1 and 1:0.075, respectively. c, UV-vis NIR spectra of HNG sheets ~1 mm thick. The normalized spectral solar irradiance density of air mass
1.5 global (AM 1.5 G) tilt solar spectrum is shown by the black broken line. d, The surface temperature rise of hydrogel samples relative to heating time
under 1 sun radiation. The different dependence between temperature and time of the HNGs revealed their different energy utilization abilities.

blank control experiment based on pure PVA hydrogels further
demonstrated the significance of the hierarchical structure of the
HNGs (Supplementary Fig. 16). The corresponding energy effi-
ciency (η) for solar to vapour generation can then be calculated
using the following formula16:
η = mh
̇ V ∕CoptP0
where ṁ is the mass flux, hV is the vaporization enthalpy of the water
in HNGs, P0 is the solar irradiation power of 1 sun (1 kW m−2), and
Copt refers to the optical concentration on the absorber surface. We
note that the vaporization enthalpy of water confined in the HNG
molecular mesh is smaller than that of bulk water. Both evaporation
measurements and differential scanning calorimetry experiments
(1) demonstrated a reduced vaporization enthalpy compared with that

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Articles Nature Nanotechnology

a b 100 5
c
Ref.14
0 Ref.15
3
Mass change (kg m–2)

80 4

Energy efficiency (%)

Ref.16

Evaporation rate
Ref.17

Evaporation rate
–1 Ref.19

(kg m–2 h–1)

(kg m–2 h–1)

60 3
Ref.20
Water 2 Ref.21
–2 HNG1 40 2 Ref.23
HNG2 Ref.24
Current study
–3 HNG3 20 1
1
HNG4
0 0
0 1,000 2,000 3,000 HNG1 HNG2 HNG3 HNG4 40 60 80 100
Time (s) Energy efficiency (%)

d ΔT pattern e f g
0 –20 Model Temperature Water transport
70
37.6 41.3
60 + +
400 315 400 0.9
21.4 21.4
Temperature (°C)

+ +
50 21.3
+

Z (μm)

Z (μm)
21.3
40 + 200 200
HNG
30 Water Internal gap 294 0.01
Micron channel (K) (μm s–1)
20
0 0
0 2,000 4,000 Polymeric network 0 200 400 0 200 400
Time (s) X (μm) X (μm)

Fig. 4 | Vapour generation under 1 sun. a,b, The mass loss of water (a) and solar vapour generation energy efficiency (b) with corresponding evaporation
rates of different HNGs under 1 sun (1 kW m−2), with pure water as the control. Each error bar represents the deviation from at least 15 data points.
c, Comparison of HNG vapour generation performance and previous reports under 1 sun. d, Plot showing the temperature of bulk water and HNG3 under
1 sun relative to irradiation time. Insets: infrared images showing the temperature distribution after irradiation times of 0, 500 and 3,600 s. e–g, Theoretical
simulation of internal gaps, micron channels and polymeric network (corresponding to molecular meshes) modelled by red oval areas, yellow narrow bars
and blue background, respectively (e), temperature distribution (f) and water transport in a HNG (g).

of pure bulk water (Supplementary Figs. 17 and 18). To explain this Mechanism for high-efficiency solar water evaporation
reduction in vaporization enthalpy, we turned to the water cluster Figure 4d compares the surface temperature of HNG3 and the bulk
theory37,38. Water can be evaporated as either a single molecule or in water relative to irradiation time. With 1 h of solar radiation, the free-
small clusters consisting of a few to tens of molecules. When water floating HNG showed a rapid temperature increase, while the bulk
molecules are confined in the molecular mesh (Supplementary water remained at a constant temperature. The temperature of the
Fig. 19), they are more likely to escape the polymer network as HNG increased from 21.3 to 37.6 °C within 500 s, and then further
small clusters rather than individual molecules (Supplementary increased to 41.3 °C within 1 h. In contrast, the temperature of bulk
Fig. 20). As such, the water is evaporated to a state with a lower water remained at ~21.3 °C after 1 h. The insets in Fig. 4d are infrared
enthalpy change than conventional latent heat. A thermodynamic photographs of cuvettes after irradiation times of 0 s, 500 s and 1 h.
analysis was also performed to demonstrate the energy balance and These results proved that the converted energy was localized in
vaporization enthalpy reduction (Supplementary Figs. 21 and 22). the HNG. In addition, to reveal the temperature distribution in the
It should be noted that for concentrated solar irradiation, further HNG, COMSOL Multiphysics software was used to simulate a fully
molecular tailoring of HNG-based materials for balanced water hydrated HNG undergoing solar radiation. The modelled structure
transport and solar adsorption is needed to achieve optimal energy is shown in Fig. 4e, where the internal gaps, micron channels and
efficiency at various solar fluxes, despite the reduced vaporization molecular meshes were simulated by broad ovals (red, with widths
enthalpy (Supplementary Fig. 23). of 150 μ​m), narrow bars (yellow, with widths of 0.2 μ​m) and quadrate
The energy efficiency of solar vapour generation is shown in background (blue) in a two-dimensional (2D) mapping of a cross-
Fig. 4b (blue points) with error bars representing the standard section, respectively. Then, a simple heat-transfer model was used to
deviation. The energy efficiency of HNG3 reached up to 94% describe the temperature distribution in the HNG39 (Supplementary
under 1 sun. In other reported state-of-the-art systems, such a Fig. 25). The simulation results of the steady-state temperature dis-
high efficiency (greater than 90%) can only be achieved via highly tribution predicted that the maximum temperature in the HNG
concentrated solar radiation (with a flux density higher than could be 315 K at the surface of polymeric network (Fig. 4f). This
4 kW m−2) (Supplementary Fig. 24). The relatively low efficiency predicted value was close to our experimental results, therefore con-
produced by HNG1 and HNG4 further proved the importance of firming the heat confinement occurring in the HNG. Additionally,
water management, which is in agreement with the results of the a biphasic mixture model was used to simulate the water trans-
heating behavior analysis shown in Fig. 3. The energy efficiency port in the HNG40. The 2D mapping of water velocity distribution
and water evaporating rate under 1 sun were key parameters for depicted a fast water transport through the internal gaps against the
evaluating the possibility of materials to generate vapour under surface water loss (Fig. 4g and Supplementary Fig. 26). Along with
ambient conditions. Thus, the performance of the developed HNG our experimental data, the surface water loss was estimated to be
was compared with recently reported materials (Fig. 4c); the devel- 0.89 μ​m s−1. The calculated water transport rate from the bottom
oped HNG achieved record high evaporation rates with a highly (Z =​ 0, corresponding the interface of bulk water and the HNG) to
efficient energy utilization14–17,19–21,23,24. the surface was 0.9 μ​m s−1; this transport was mainly supported by

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Nature Nanotechnology Articles
a 104 b 4
3 Before desalination
10

Evaporation rate (kg m–2 h–1)

After desalination
102 3

101

Salinity (‰)
WHO
100 2 Baltic sea
10–1 EPA World sea
Dead sea
10–2 1

10–3

10–4 0
Baltic sea World sea Dead sea 0 10 20 30 40 50
Time (h)
c 106 d 4
Before desalination
5
10 After desalination

Evaporation rate (kg m–2 h–1)

3
Concentration (mg l–1)

104

103 Day 1 Day 28

Mass change (kg m )

Mass change (kg m )

0 0

–2

–2
2
–1 –1
102
–2 –2
101
1
–3 –3
100
0 3,600 0 3,600
Time (s) Time (s)
10–1 0
Na+ Mg2+ K+ Ca2+ 0 10 20 30
Time (days)

Fig. 5 | Solar desalination performance and durability of the HNGs. a, The salinities of three artificial seawater samples before and after desalination using
HNG3. The broken lines refer to the World Health Organization (WHO) and US Environmental Protection Agency (EPA) salinity standards for drinkable
water. b, Solar endurance test results of a HNG continuously exposed to 1 sun for 50 h. c, Measured concentrations of four primary ions in an actual seawater
sample before and after desalination. d, Water evaporation rates of HNGs immersed in seawater for a long time; the results of this solar desalination test
demonstrated the salt durability of the HNGs. Insets: typical solar vapour generation behaviour on exposure to seawater for 1 day and 28 days.

internal gaps, while the uniform water diffusion near the evaporat-
ing surface was assisted by the micron channels.
Laboratory and outdoor solar desalination
To demonstrate the solar desalination capability of the optimized
HNG3, three brine samples with representative simulated salinities
(g of dissolved salt per kg seawater (‰))—Baltic sea (lowest salin-
ity, 8‰), World sea (average salinity, 35‰) and Dead sea (highest
salinity, 100‰)41—were used and carefully tracked via a conduc-
tivity test (Supplementary Fig. 27). After desalination, the salini-
ties of the artificial brine samples were all significantly decreased
(by approximately four orders of magnitude; Fig. 5a), and were
approximately two orders of magnitude below the drinking water
standards defined by the World Health Organization (1‰) and
the US Environmental Protection Agency (0.5‰)42. Solar dura-
bility is another important aspect of solar desalination. The water
evaporation rate, which is independent of salinity, was maintained
after continuous exposure for 50 h (Fig. 5b). Furthermore, a real
seawater sample (from the Gulf of Mexico) was used for desalina-
tion via the HNG. It was found that the concentrations of all four
primary ions (Na+, Mg2+, K+ and Ca2+) originally present in the
seawater were significantly reduced (Fig. 5c), and were below the
values typically obtained through membrane-based (10–500 mg l−1)
and thermal distillation-based (1–50 mg l−1) seawater desalination
techniques42,43. As the solar evaporator needs to be in contact with
seawater for a long period of time during desalination, the salt dura-
bility of the HNGs is important for practical applications. As shown
in Fig. 5d, the HNG presented a stable evaporation rate under 1 sun
irradiation on exposure to the seawater sample for up to 28 days.
Such results indicate that the HNG is potentially reliable for practi-
cal long-term solar desalination.
A solar water purification prototype based on the optimized
HNG3 was placed on the roof of the Engineering Teaching Center at
the University of Texas Austin campus. Here, a HNG3 sample with
a diameter of ~20 cm and thickness of 2 cm (Fig. 6a) was floated in
a container of brine, which was set on the upper layer of the proto-
type (Fig. 6b). The evaporated water condensed on the transparent
condenser (Fig. 6b), and the water condensate flowed to the bottom
of the prototype (Fig. 6b). To demonstrate the possibility of con-
tinuous water purification, the water receiver of the prototype was
connected (Fig. 6b,c) to the brine tank and to a purified water flask
(Fig. 6c); this set-up simulated the functional parts of practical solar
water purification equipment or plants. The experiment was carried
out from 08:00 to 20:00 under natural sunlight with an average solar
heat flux of ~0.7 kw m−2 (Fig. 6d), and the solar irradiation, inter-
nal humidity, air temperature, salt-water temperature and HNG3
surface temperature were carefully traced to quantitatively evalu-
ate the utilization efficiency of natural sunlight. The ample sunlight
enabled an average water purification rate of ~1.6 l m−2 h−1 (Fig. 6e,
blue curve). As shown in Fig. 6e, the surface temperature of the
HNG sample increased to ~55 °C, indicating a weakened evapora-
tion cooling effect, hence reduced evaporation, compared with that
in laboratory test condition. Such a phenomenon can be attributed
to the saturated internal humidity of the closed system (Fig. 6e),
which slightly restrained water vaporization (see Supplementary
Fig. 28 for details). The brine maintained a relatively low temperature
of ~30 °C (Fig. 6e), even when the internal air and condenser were
heated to ~45 and ~40 °C, respectively, indicating an effective heat-
ing localization effect on the surface of the HNG sheet. Additionally,
the data collected during non-ideal conditions (Supplementary
Fig. 29) indicated that the HNG enabled solar water purification
during periods of low and/or varying solar irradiation, revealing

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Articles Nature Nanotechnology

a b c

Transparent condenser

Inlet (2)
HNG vapour pipe
generator
(1)

Brine

(3)
Purified Outlet pipe
water
(1) Solar vapour system
10 cm
(2) Brine tank
(3) Purified water flask

d 1.0 e 60
600
HNG surface 100
500
Irradiation (kw m–2)

Purified water (ml)

0.8 50

Temperature (°C)
Internal air
400
RH
0.6 300 40
Condenser (%)
200
0.4 100 30
Brine
40
0
0.2 20
0 1 2 3 4 5 6 7 8 9 10 11 12
0

0
:0

:0

:0

:0

:0

:0

:0
08

10

12

14

16

18

20

Time (h)
Time
f
Electrodes
Ohmic value

Water
sample
Seawater Purified water Domestic water

Fig. 6 | Outdoor solar water purification using HNGs in natural sunlight. a, Photograph of a large-scale HNG sheet. b,c Schematic of a water receiver
based on a HNG (b) for a prototype solar water purification system simulating the practical water purification equipment (c). The HNG floats on brine in a
container that is located in a holder with meshes. The vapour is condensed via the transparent condenser and flows to the bottom of the prototype, where
the purified water is stored. Brine is supplied and fresh water collected at optimum rates through the inlet pipe and outlet pipe, respectively. A sustained
water purification system was achieved under natural sunlight. d, Solar radiation recorded over time on a sunny day from 08:00 to 20:00. e, The amount
of purified water during 12 h of outdoor solar desalination (solid blue line) with careful tracing of the internal relative humidity (RH; background colour
map), and the temperature of the HNG surface (red broken line), internal air (green broken line), condenser (violet broken line) and brine (orange broken
line). f, Evaluation of water purity using a multimeter with a constant distance between electrodes. The results demonstrated a high purity of purified
water, similar to that of domestic water.

its significant potential for practical applications. The water qual- the hierarchical water pathways in the HNGs, providing expedited
ity can be directly represented by the ohmic value obtained from water absorption from bulk water and tunable water content in the
a resistance test using a multimeter at constant distance between polymeric network. The solar energy conversion is induced by the
electrodes (Fig. 6g). The real seawater, purified water and domestic light-absorbing polymer penetrating the molecular meshes of the
water (from an urban water-supply system of Austin, Texas, United HNG, which provides an efficient in situ energy utilization system
States) showed resistance values of 0.08, 1.4 and 1 MΩ​, respectively, for powering water evaporation with significantly reduced vapor-
indicating effective purification of natural seawater. ization enthalpy. These unique properties of the HNGs enabled a
solar vapour generation rate of 3.2 kg m−2 h−1, with an energy effi-
Conclusions ciency of up to ~94%. As demonstrated by a prototype solar water
As detailed above, highly efficient solar vapour generation was purification system, the HNG was able to produce fresh water with
achieved due to effective energy confinement based on tailored a daily yield of 18–23 l m−2 under natural sunlight. Apart from the
water transport in HNGs. The water distribution can be regulated by demonstrated solar water purification system, the HNG-based solar

494 Nature Nanotechnology | VOL 13 | JUNE 2018 | 489–495 | www.nature.com/naturenanotechnology

© 2018 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
Nature Nanotechnology
energy harvesting system may be used for many other applications,
including environmental cooling, water and moisture management,
and pollution abatement.
Methods
Methods, including statements of data availability and any asso-
ciated accession codes and references, are available at https://doi.
org/10.1038/s41565-018-0097-z.
Received: 22 May 2017; Accepted: 19 February 2018;
Published online: 2 April 2018
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Acknowledgements
G.Y. acknowledges financial support from a Sloan Research Fellowship, a Camille
Dreyfus Teacher-Scholar Award, and a National Science Foundation award (NSF-
CMMI-1537894). Molecular dynamics simulations were performed using a Summit
supercomputer supported by the NSF (NSF-ACI-1532235).
Author contributions
G.Y. supervised the entire project. G.Y., F.Z., X.Z. and L.Q. conceived the idea
and co-wrote the manuscript. F.Z. and X.Z. performed materials fabrication and
characterization and carried out data analyses. F.Z. and Y.S. performed the numerical
simulations. X.Q., X.Z. and R.Y. performed the molecular dynamics simulations and
differential scanning calorimetry measurements on the gel samples. M.A. and S.M.
assisted in experimental work. R.Y. and L.Q. assisted in the design of experiments and
interpretation of results. All the authors discussed the results and commented on the
manuscript.
Competing interests
The authors declare no competing interests.
Additional information
Supplementary information is available for this paper at https://doi.org/10.1038/
s41565-018-0097-z.
Reprints and permissions information is available at www.nature.com/reprints.
Correspondence and requests for materials should be addressed to R.Y. or L.Q. or G.Y.
Publisher's note: Springer Nature remains neutral with regard to jurisdictional claims in
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Methods
Preparation of the HNGs. For preparation of the HNGs, PVA (Mw =​  15,000),
glutaladehyde and PPy of various corresponding molar mass were dissolved in
deionized water. An appropriate amount of HCl was subsequently added. The
gelation was carried out for 2 h. The obtained PVA gel was immersed in deionized
water overnight to obtain pure HNGs. The purified HNGs were frozen by liquid
nitrogen and then thawed in deionized water at 30 °C. The freeze–thaw process was
repeated ten times. Finally, the obtained HNG samples were freeze dried.
Solar vapour generation experiments. The water evaporation performance
experiments were conducted in the laboratory using a solar simulator (AbetTech,
M-LS Rev B) outputting a simulated solar flux of 1,000 W m–2 (1 sun). The solar
flux was measured using a thermopile (Newport, 818SL) connected to a power
meter (Newport, 1916-R). Because the solar flux varies across the beamspot, and
the thermopile detector is ~1 cm2 in size, the HNG was cut into small pieces with
a surface area of 1 cm2 to ensure an accurate power input. A HNG chip (~0.5 cm
thick) was transferred and floated on pure water (or brine for the desalination
tests) in a glass cuvette that was placed in the beamspot with a solar flux of 1 sun.
The mass of water loss was measured using a laboratory balance with 0.1 μ​g
resolution and calibrated to weights heavier than the total weight of the set-
up. Before illuminating the set-up, the evaporation rate in dark conditions was
© 2018 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
Nature Nanotechnology
measured for 1 h. The dark-condition evaporation rate was subtracted from the
solar-illuminated evaporation rate. All evaporation rates were measured after
stabilization under 1 sun for 10 min.
Characterization. The morphology and microstructure of the samples were
observed by SEM (Hitachi, S5500) operating at 5 kV. Before observation, the
HNGs were freeze dried for 24 h. The FTIR spectra of the HNGs were recorded
using a FTIR spectrometer (Thermo Mattson, Infinity Gold FTIR) equipped with
a liquid nitrogen-cooled narrowband mercury cadmium telluride detector, using
an attenuated total reflection cell equipped with a Ge crystal. To understand the
mechanical properties of the HNGs, rheological experiments were performed (AR
2000EX, TA Instrument) using a parallel plate on a peltier plate in the frequency
sweep mode. Absorption spectra, transparency and reflectance were recorded
using a UV–vis NIR spectrometer (Cary 5000) with an integrating sphere unit
and automated reflectance measurement unit. The measurements were corrected
by baseline/blank correction through the control software of UV–vis NIR
spectrometer. The concentration of ions was tracked by inductively coupled plasma
mass spectrometry (Agilent 7500ce) with dilutions in 2% HNO3 to make the
loaded ion concentration below 10 ppm.
Data availability. The data that support the findings of this study are available
from the corresponding authors upon reasonable request.
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