Carbon 195 (2022) 263e271

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Carbon-supported nano tungsten bronze aerogels with synergistically

enhanced photothermal conversion performance: Fabrication and
application in solar evaporation
Guiqin Li a, Qing Wang a, Jia Wang a, Jianyong Ye a, Wenwu Zhou a, Jiang Xu a,
Sheng Zhuo a, Weifan Chen a, b, c, *, Yue Liu a, c, **
a
School of Physics and Materials Science, Nanchang University, Nanchang, 330031, PR China
b
Jiangxi Sun-Nano Advanced Materials Technology Co. Ltd., Ganzhou, 341000, PR China
c
Rare Earth Research Institute, Nanchang University, Nanchang, 330031, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Solar interfacial evaporation is an effective and sustainable strategy to solve the shortage of fresh water.
Received 17 January 2022 Nowadays, fully converting the near-infrared light with significant thermal effect, and reducing the
Received in revised form energy loss in evaporation stage are the key factors to achieve higher evaporation rate. Herein, the nano
17 March 2022
cesium tungsten bronze (Cs0.32WO3) with exceptional near-infrared absorption property was loaded on
Accepted 8 April 2022
Available online 13 April 2022
reduced graphene oxide-carbon nanotubes (rGO-CNTs) composite aerogel, drastically enhancing the
evaporation efficiency from 61.0% to 85.9%, which can be explained by the remarkable synergistic effect
between rGO-CNTs and nano Cs0.32WO3 in improving the photothermal conversion performance. As a
Keywords:
Nano tungsten bronze
result, the solar evaporators assembled by the fabricated rGO-CNTs-Cs0.32WO3 aerogels and corn straw
Carbon aerogel grooves achieved an evaporation rate of 1.93 kg m
2 h
1, exceeding the previously-investigated carbon
Photothermal conversion aerogels/foams, natural plants and tungsten-based compound systems. The characterization results
Synergistic enhancement reveal that the loading of nano Cs0.32WO3 contributes to the partial restoration of p-conjugated structure
Solar steam generation in rGC, increasing solar absorption and the corresponding thermal energy released by the lattice vi-
bration. Meanwhile, the oxygen vacancies and carrier density of Cs0.32WO3 nanoparticles increase after
compositing with rGC, which further enhances the local surface plasma resonances (LSPR) effect.
Significantly, the hydrophilic functional groups and excellent wettability of composite aerogel and corn
straw play crucial effect in accelerating water transport, activating water molecules and reducing
evaporation energy consumption. In a word, the unique construction of rGO-CNTs-Cs0.32WO3 aerogels
presents a novel approach for the design of solar-driven freshwater production system, the application
expansion of nano tungsten bronze and carbon aerogels.
© 2022 Elsevier Ltd. All rights reserved.

1. Introduction mainly focused on increasing solar-heat conversion efficiency

[5e7], regulating water transport path [8], reducing heat transfer
Solar-driven interfacial evaporation (SDIE) offers a promising loss and evaporation enthalpy [9,10]. Among them, the design of
and cost-effective way for seawater desalination, and it has been evaporation system, the optimization of the properties and mi-
applied for alleviating the global clean water shortages [1e4]. In crostructures of photothermal conversion material have become
recent years, with the gradual popularization of SDIE technology, the core challenges to achieve stable and efficient freshwater pro-
the optimization strategies of interfacial evaporation system are duction and promote the progress of SDIE device.
As a clean and sustainable resource, the energy in the near-
infrared (NIR) band accounts for the highest proportion (52%) of
** Corresponding author. School of Materials Science and Engineering, Nanchang the sunlight which radiates to the earth surface [11,12], and the
University, Nanchang, 330031, PR China. thermal effect caused by the absorption and conversion of NIR
* Corresponding author. School of Materials Science and Engineering, Nanchang light is more significant. Meanwhile, NIR light can penetrate
University, Nanchang, 330031, PR China. clouds and be less affected by the changes of climate and
E-mail addresses: [email protected] (W. Chen), [email protected] (Y. Liu).

https://doi.org/10.1016/j.carbon.2022.04.023
0008-6223/© 2022 Elsevier Ltd. All rights reserved.
G. Li, Q. Wang, J. Wang et al. Carbon 195 (2022) 263e271

environment. Therefore, the metals or semiconductors with sur- of rGO and CNTs were prepared by hydrothermal method, then the
face plasmon resonance (SPR) effect, such as Al [13], Ag [14], Au cesium tungsten bronze nanoparticles were loaded on the surface
[15], CuS [16], TiOx [17], WOx [18] and MxWO3 (tungsten bronze) of rGC by impregnation process. Finally, the carbon-based nano
[19] have attracted much attention because they are more tungsten bronze aerogels (rGC-CWO) were synthesized by freeze-
conductive to the thermal conversion of NIR light. As a kind of drying method. Afterwards, the rGC-CWO aerogels would be
nano-material with excellent NIR photothermal conversion per- embedded in the corn straw (CS) substrate to assemble the rGC-
formance, the nano-tungsten bronze, especially the CsxWO3 CWO/CS evaporators. Moreover, combined with the analysis of
(CWO), has emerged and developed rapidly in the field of pho- the microstructure, vapor generation performance and chemical
tothermal therapy [20]. Moreover, based on the topology trans- groups, the cooperative mechanism of the photothermal conver-
formation technology of mechanochemical reaction method sion effect between rGO-CNTs and CWO would also be further
developed by our group [21], the cost of CWO has been further explored.
reduced to meet the needs of large-scale production and appli-
cation of SDIE devices. It was also reported that the addition of
2. Results and discussion
nano-tungsten bronze could make the rTAC porous fiber mem-
branes achieve a strong NIR photothermal conversion effect, and
Fig. 1a schematically summarizes the synthesis route in several
the evaporation rate was significantly improved [22]. However,
steps: Firstly, the rGC aerogels were prepared by hydrothermal and
due to the fewer incident light paths and direct contact with the
lyophilization methods, and in the early exploration, it was also
bulk water, the light absorption effect has been limited and a large
obtained through the optical spectral data (Fig. S1) that the rGO-
amount of heat conduction loss was also unavoidable, which
3CNTs showed the highest absorption, so the rGC aerogels pre-
would be not conducive to the application promotion of CWO and
pared in this paper would maintain this ratio. Subsequently, the
the efficient utilization of solar energy.
composition of CsxWO3 was determined to be Cs0.32WO3 by XRD
Compared with 2D materials, the 3D materials based on cross-
analysis (Fig. S2) and the Cs0.32WO3 nanoparticles were self-
linked network structure have larger evaporation area and stron-
assembled on the surface of rGC aerogels by electrostatic force [41]
ger light absorption property. The common 3D materials include
(Fig. 1b). Furthermore, Fig. 1c also proved that the temperature in-
nanocellulose foams [23], plants [24e26], graphene aerogel
crease trend of rGC-5%CWO was faster than that of rGC under 1 sun,
[27e29] and metal-organic frames (MOF) [30]. Among them, gra-
and the temperature difference was as high as 13.6  C after only
phene aerogel has the advantages of low density, more pores and
4 min (Fig. 1d). From above phenomenon, the loading of cesium
less pollution [31]. Notably, the carbon-based composite aerogels
tungsten bronze evidently enhanced the photothermal conversion
constructed from graphene and carbon nanotubes (CNTs) exhibit
performance of rGC aerogels. Additionally, the test video in Movie. S1
lower thermal conductivity, which enabling a more energy-
demonstrated that the rGC-CWO aerogels had good elasticity. The
efficient mode of local thermal evaporation. In addition, the
relevant durability tests (Fig. S3) also showed that after 10 evapo-
excellent visible light (Vis) absorption performance of carbon-
ration cycles, the composite aerogel still maintains a high elasticity.
based aerogels can make up for the shortcoming of nano-
The corn straw was washed and dried, then it would be made into a
tungsten bronze material and ensure the full conversion of all so-
groove shape (Fig. 1e), and the rGC-CWO aerogels were wrapped in
lar spectra [32]. Despite the similarities between WOx and CWO in
corn straw component, which will be used to complete solar water
microstructures [33,34], WOx and CWO are analogical in light ab-
evaporation by the combined experimental apparatus (Fig. 1f and g).
sorption property, and it has been confirmed that W18O49/rGO
Under the premise of invariable rGC and CS, it would be ex-
(reduced graphene oxide) can effectively absorb full-spectrum
pected to achieve a higher evaporation rate by changing the CWO
sunlight and obtain stronger photothermal conversion properties
loading content of rGC-CWO aerogels, thus breaking the theoretical
[35], the correlation between CWO and carbon-based materials
evaporation rate limit. Furthermore, as shown in Fig. 1g, the bea-
(rGO, CNTs) remained to be clarified.
kers equipped with rGC-x%CWO/CS (x ¼ 0, 10, 18.9, 25.6, 31.3) were
Although the current researches are mainly focused on
placed directly under the solar simulator, while a high precision
improving the photothermal conversion efficiency, while the
balance was used to monitor the change of water quality in real
reducing of the evaporation energy consumption will be an effec-
time, and the surface temperature of the evaporator was recorded
tive way to break through the theoretical upper limit of evaporation
with an IR camera (detailed in Supporting Information: Additional
rate [36]. In recent years, it has been reported that the existence of
experimental methods).
polymer cross-linking structure or special chemical functional
The classical curves of time-dependent water mass loss are
groups in SDIE materials was helpful to reduce the evaporation
provided in Fig. 2a, and the evaporation rates were calculated ac-
enthalpy [37,38]. Accordingly, the influence of the surface chemical
cording to the slope of the curves (these data have subtracted the
groups of carbon-based aerogels on the evaporation enthalpy
evaporation rate in the dark environment which was measured in
needs to be further explored. In addition, the hydrogel systems
Fig. 2e). As a result, the net evaporation rates of rGC-x%CWO/CS
based on polyvinyl alcohol and chitosan were developing rapidly,
(x ¼ 0, 10, 18.9, 25.6, 31.3) are 1.37, 1.64, 1.93, 1.62, and
while the systematic researches based on natural plant cellulose
1.34 kg m
2 h
1, respectively, which are much higher than that of
were relatively few. It can be found from the previous studies that
seawater (0.32 kg m
2 h
1). Obviously, as the increase of the
the cellulose nanofibers formed by chain polysaccharides polymers
amount of CWO, the evaporation rate increases at first and then
in corn straw not only had super toughness and abundant hydro-
decreases, and the rGC-18.9%CWO/CS is the turning point. Mean-
philic groups [39], but also exhibited low thermal conductivity and
while, the IR images of evaporators also indicate that rGC-18.9%
easy processing characteristics [40], which contributed to the
CWO/CS has higher photothermal rate and could maintain a
construction of heat insulation environment in SDIE devices.
higher temperature of 39.6  C after 1 h irradiation (Fig. 2b).
Therefore, the exploration of corn straw substrate is of great sig-
To evaluate the effect of solar energy-steam conversion
nificance to accelerate the development of evaporation efficiency
comprehensively, the evaporation efficiency (h) is calculated by
and circular economy.
formula (1), which has the same definition as that in recent re-
In this paper, the carbon-based hydrogels (rGC) that composed
searches [1,42].

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G. Li, Q. Wang, J. Wang et al. Carbon 195 (2022) 263e271

Fig. 1. (a) The fabrication process of rGC-CWO aerogel. (b) Schematic diagram of electrostatic adsorption of Cs0.32WO3 nanoparticles on the surface of rGC aerogels. (c) Surface
temperature variation over heating time, and (d) infrared thermal images of rGC and rGC-5%CWO aerogels under different illumination time (0 s, 120 s, 240 s). (e) Optical photos of
rGC-5%CWO and rGC-5%CWO/CS evaporators. (f) The structural assembly illustration of rGC-CWO/CS evaporator. (g) The diagram of the solar water evaporation installation. (A
colour version of this figure can be viewed online.)

Where the evaporation rate (rwater) of the solar steam generator is

_
mEv determined by the evaporation efficiency (h) and the water
h¼ (1) vaporization enthalpy (DHvap) [43].
Copt qi

where m_ represents the evaporation rate at the steady state, EV is

h  1kW,m
2
the energy consumption of water evaporation with rGC-CWO/CS DHvap ¼ (2)
rwater
system based on the dark experiment data (Fig. 2e), Copt is the
optical concentration, and qi means the nominal direct solar irra- The water evaporation enthalpy of the bulk water is 2450 J g
1
diation (1 kw,m
2). After calculation, the evaporation efficiency of [44,45], so the theoretical limit of evaporation rate is
rGC-x%CWO/CS (x ¼ 0, 10, 18.9, 25.6, 31.3) is 61.0%, 73.1%, 85.9%, 1.47 kg m
2 h
1 under 1 sun. The previous works which used
72.2% and 59.7% respectively. It can be noted that the evaporation hydratable light-absorbing hydrogel [38] and polymer [37] have
efficiency of all rGC-x%CWO/CS evaporators is better than that of reduced the DHvap, and a higher evaporation rate can be achieved
rGC/CS, and the value of rGC-18.9%CWO/CS shows the highest under the same or even lower evaporation efficiency. It can be
(Fig. 2c). Comparing with other carbon aerogels/foams, natural calculated from Fig. 2e that the evaporation energy consumption of
plants and tungsten-based (WOx) material systems in previous rGC-18.9%CWO, CS, rGC-18.9%CWO/CS are 1371, 1656, and
researches, the carbon supported-nano cesium tungsten bronze 1604 J g
1, and these enthalpy values were lower than those of DSC
aerogels synthesized in this work own significant advantage in measurement of energy consumption (Fig. 2h and Table S3). This
evaporation rate (Fig. 2d and Table S1). result should be attributed to the water activation effect of hydro-
On this basis, the solar irradiation was removed, and the water philic groups [37], including the substantial OeH groups and a
vaporization energy consumption of each system, which means the small number of C]O groups (-COOH) that originated from rGC-
equivalent vaporization enthalpy, can be deduced by comparing the 18.9%CWO and CS (Fig. 2f). Due to the natural cellulose network
evaporation rate of rGC-18.9%CWO, CS, and rGC-18.9%CWO/CS of corn straw, the water in the hydrated cellulose network has been
samples in the dark experiment and combining with formula (2). classified into three types: free water (FW), intermediate water
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G. Li, Q. Wang, J. Wang et al. Carbon 195 (2022) 263e271

Fig. 2. The comparison of rGC-x%CWO/CS (x ¼ 0, 10, 18.9, 25.6, 31.3) evaporators: (a) the mass loss of water, (b) infrared thermal images of surface temperature of rGC/CS, rGC-18.9%
CWO/CS, rGC-31.3%CWO/CS evaporators under different irradiation time. (c) The evaporation rate and evaporation efficiency of corresponding systems. (d) Comparison of rGC-18.9%
CWO/CS with carbon aerogels/foams, natural plants and tungsten-based systems in previous studies. (e) Dark evaporation experiments of CS, rGC-18.9%CWO and rGC-18.9%CWO/CS
systems. (f) The FTIR analysis of corn straw and rGC-18.9%CWO aerogel. (g) DSC curves and the fitted curves that recording the melting behavior of water frozen in rGC-18.9%CWO,
water, and corn straw samples. (h) Thermograms of rGC-18.9%CWO and corn straw, the magnitudes of the DSC signal were proportional to the heat flow during the measurements.
(i) UVeViseNIR absorption spectra of rGC-x%CWO samples. (A colour version of this figure can be viewed online.)

(IW), and bound water (BW), respectively [38]. BW has strong 1.90 kg m
2 h
1, demonstrating that the rGC-18.9%CWO/CS evap-
interaction with functional groups in cellulose chains, and FW has orator has good durability. Moreover, the data comparison of Fig. S5
no interaction with cellulose chains. Besides, the IW between BW reveals that the surface temperatures of rGC and rGC-18.9%CWO
and FW exhibits weak interaction with its surrounding molecules. stabilized after 50 min of evaporation. The temperature difference
The formation of IW is so beneficial to evaporation that the between the two samples remains at about 3  C for the next 4 h
equivalent evaporation enthalpy value would be decreased obvi- without significant changes. The results of simulated seawater solar
ously. As a result of DSC measurement (Fig. 2g), there exists sub- desalination show that the concentration of major ions (Naþ, Mg2þ,
stantial intermediate water in rGC-18.9%CWO aerogel and the Kþ, Caþ) in seawater decreases by 2e4 orders of magnitude after
melting point showed the subzero tendency. Furthermore, there evaporation, the ion concentration in collected freshwater is very
exist 35.3% IW and 49.6% FW in corn straw, which is tally with the low (Fig. S6), proving that the composite aerogel evaporator has
data of the dark experiment and DSC measurement of energy good desalination effect.
consumption (Fig. 2h, Tables S2 and S3). In summary, apart from the evaporation energy consumption
Considering that the durability of solar evaporator is an reduction effect of rGC and CS, the loading of CWO nanoparticles
important index to evaluate the feasibility of its practical applica- could enhance the photothermal conversion effect of rGC aerogels,
tion, under the same condition, 30 cycles of solar steam generation and rGC-18.9%CWO has the best evaporation rate and evaporation
experiments were carried out on the rGC-18.9%CWO/CS evaporator. efficiency. It is speculated that there may be two reasons for the
As shown in Fig. S4, the evaporation rate of each cycle is close to above phenomena: on the one hand, the synergistic effect between

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G. Li, Q. Wang, J. Wang et al. Carbon 195 (2022) 263e271

carbon and cesium tungsten bronze can promote the optical ab- the uniform contact and the interaction between CWO nano-
sorption and photothermal conversion. On the other hand, the particles and rGC. Fig. 3g demonstrates the wettability test of rGC-x
composite amount of cesium tungsten bronze could affect the %CWO (x ¼ 0, 10, 18.9, 31.3) aerogels and corn straw. The rGC, rGC-
porosity of the rGC-CWO aerogels, which will influence the water 10%CWO, and rGC-31.3%CWO aerogel require 0.10 s, 0.31 s and
supply performance. 0.53 s, respectively, to absorb water droplets, while the rGC-18.9%
In view of the above speculation, the transmittance and reflec- CWO aerogel takes 0.62 s and the straw consumes 3.41 s. The re-
tance curves of rGC-x%CWO (x ¼ 0, 10, 18.9, 25.6, 31.3) were sults indicate that the rGC-CWO aerogels have excellent wettability
measured by UVeViseNIR spectrometer from wavelength performance. Although the wetting rates of rGC-CWO aerogels are
300e2500 nm, and the absorption data was calculated by formula slightly decreased compared with rGC aerogel, it indicates that the
A ¼ 1-R-T. As shown in Fig. 2i, comparing with rGC aerogel (95%), influence of loaded CWO particles on the pore morphology will be
the average absorption of rGC-x%CWO (x ¼ 10, 18.9, 25.6, 31.3) reflected in the water supply capacity, which is also related to the
reaches 96.4%, 97.2%, 96.6%, and 96.7%, respectively (integrated by pore size.
AM 1.5 standard). In addition, the light irradiation experiment at Subsequently, the porosity and specific surface area of rGC-x%
selective wavelengths demonstrates that compared with the Vis CWO aerogels are characterized. As illustrated in Fig. 3h, there are
source, the difference in absorbance and temperature between mesopores (D: 2e50 nm) and macropores (D > 50 nm) in rGC-x%
rGC-18.9%CWO and rGC aerogels are significantly greater under NIR CWO aerogels (x ¼ 0, 10, 18.9, 31.3), then it can be found that the
light (Figs. S7 and S8). Combined with previous reports [19,46], it proportion of pores in the 2e4 nm range and the pore volume (dv/
indicates that the loaded CWO nanoparticles enhance the photo- dD) of rGC-x%CWO aerogels gradually decrease with CWO content
thermal conversion performance mainly relying on the localized increasing, which is attributed to the aggregation effect of CWO
plasmonic resonances effect. nanoparticles around the pores would affect the pore structures in
Fig. 3a~f show the morphologies of rGC-CWO aerogels. All aer- rGC aerogels, especially near the edges of the pores (Fig. 3e and f).
ogels exhibit an interconnected pore structure on the top and side Furthermore, as demonstrated in Fig. 3i, the specific surface areas of
views. This interleaved structure is beneficial to the enhancement rGC-x%CWO aerogels (x ¼ 0, 10, 31.3) are 77.86, 62.67 and 59.09 m2/
of multiple scattering effects, thus improving the broad-spectrum g, respectively, while the rGC-18.9%CWO aerogel has the smallest
absorption [47]. The CWO nanoparticles are mainly distributed on specific surface area and average pore volume (57.55 m2/g,
the rGO sheets (Fig. 3e and f and S9). Comparing Fig. 3e and f, it can 0.240 cm3/g). The specific surface area shows a similar decreasing
be found that the CWO particles in rGC-18.9%CWO aerogel are more trend with the increase of CWO content. Considering that the
dispersed, but the excessive CWO particles in rGC-31.3%CWO aer- samples in the porosity test need to be mashed, the pore structure
ogel tend to agglomerate near the pores, which is not conducive to of aerogel may be damaged and the analysis of specific surface area

Fig. 3. (a~f) The surface morphologies and cross-section morphologies of rGC, rGC-18.9%CWO and rGC-31.3%CWO. (g) Hydrophilicity test of CS and the rGC-x%CWO (x ¼ 0, 10, 18.9,
31.3) aerogels. (h) The curves of pore size distribution. (i) The comparison of specific surface area and average pore volume of rGC-x%CWO (x ¼ 0, 10, 18.9, 31.3). (A colour version of
this figure can be viewed online.)

267
G. Li, Q. Wang, J. Wang et al. Carbon 195 (2022) 263e271

and pore size will be disturbed. Therefore, the water supply per- With the aim to confirm the chemical composition and element
formance should be tested for in-depth analysis of the relationship state of the pure Cs0.32WO3, rGC and rGC-18.9%CWO, Raman and
between structure and evaporation performance. XPS spectrum analysis were studied. Fig. 4a displays that both the G
Combining the relevant data of Fig. 3 with the water supply and D peaks of rGC-18.9%CWO are shifted to a higher region
performance test (Fig. S10), it can be found that the rGC with a compared with rGC. The ID/IG ratio of rGC is also decreased after
larger average pore volume has the highest saturated water con- loading CWO (0.86 / 0.83), indicating partial recovery of the
tent. The water supply rate and saturated water content of rGC- peconjugated framework [51]. This change may be influenced by
CWO aerogels gradually decrease as the CWO content increases. the electrostatic interaction between CWO nanoparticles and rGC.
On the one hand, due to the rGC sample lacks the heat support from Besides, there are two characteristic peak bands (900-980 cm
1
the photothermal conversion by CWO particles, and the excessive and 600-850 cm
1) rGC-18.9%CWO, which corresponds to the W]
water content leads to increasing the heat loss to the bulk water via O and OeWeO stretching modes, respectively [52]. Fig. 4b shows
water stream [48], so the evaporation rate of rGC aerogel is lower. the C 1s spectrum of rGC and rGC-18.9%CWO. The C 1s peaks of rGC
On the contrary, the smaller average pore volume of rGC-18.9%CWO are located at 284.4 eV, 285.4 eV, and 287.2 eV, corresponding to
aerogel allows the water supply rate to be moderated and the CeC, CeO and C]O, respectively. While the C 1s peaks of rGC-18.9%
saturated water content to be lower [49,50], so the heat loss CWO are located at 284.4 eV, and 285.7 eV, corresponding to CeC
transferred with the water flow is reduced. Besides, the heat and CeO, respectively. The proportion of C]O bond is very small
generated by the photothermal conversion of CWO nanoparticles and can be ignored.
provides additional support, and the water between the pores can The chemical states of the tungsten element (W 4f) of Cs0.32WO3
be evaporated in time. On the other hand, as the excessive increase and rGC-18.9%CWO are obtained from the high-resolution XPS
of CWO content (x%>18.9%) can lead to particle agglomeration profiles as shown in Fig. 4c. The tungsten curve of Cs0.32WO3 can be
around the pores, the contact area between CWO particles and rGC fitted as two spin-orbit doublets W 4f7/2 and W 4f5/2 with an in-
will be reduced and the interaction may be affected. Moreover, the terval of about 2.1 eV. The peaks of 34 and 36.4 eV are related to
heat is too concentrated near the agglomerated particles, and the W5þ, and those of 35.7 and 37.8 eV are indexed to W6þ, which
water in the area with fewer CWO particles cannot get heat in time, confirms that partial W6þ are reduced to W5þ [53]. As for rGC-18.9%
which eventually leads to another decrease in evaporation rate. CWO, the peaks at 34 and 36.1 eV, 35.4 and 37.5 eV are associated
This can be corroborated by the differences in surface temperature with W5þ and W6þ, respectively. Furthermore, the percentage of
and evaporation performance (Fig. 2b and c). Overall, the variation W5þ increases from 11.2% to 13.3%. The presence of low-valent W
of CWO content affects both the microporous structure and water species (W5þ) and their increased ratio demonstrate that the plenty
supply performance of rGC-CWO aerogels. In order to maintain of oxygen vacancies and localized electrons in CWO nanoparticles,
more efficient evaporation, the CWO content should be kept within which leads to an LSPR effect [54]. As mentioned in Fig. 4d, the
a certain range. peaks located at 531.8 eV (oxygen vacancies, OVs) in the Cs0.32WO3

Fig. 4. (a) Raman spectra of rGC and rGC-18.9%CWO. High resolution XPS spectra of Cs0.32WO3 and rGC-18.9%CWO (b) C 1s, (c) W 4f, (d) O 1s. (A colour version of this figure can be
viewed online.)

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G. Li, Q. Wang, J. Wang et al. Carbon 195 (2022) 263e271

and rGC-18.9%CWO could be attributed to the O atoms in the vi- stronger local thermal effect for water evaporation. To sum up, as
cinity of an oxygen defect or vacancy. Notably, the peak intensity of illustrated in Fig. 5c, a synergy is formed between the CWO nano-
OVs increased after the CWO nanoparticles are supported by rGC, particles and rGC, and they mutually benefit from each other, thus
and the more oxygen vacancies is beneficial to an increased carrier enhancing the photothermal conversion performance of rGC-CWO
density, resulting in a broad visible/NIR absorption and stronger composite aerogel.
LSPR effect [55]. Thus, the rGC-18.9%CWO aerogel with an Based on the previous data (Fig. 2aec), the solar water evapo-
enhanced LSPR effect displays remarkably higher photothermal ration test of CWO-y% rGC/CS (y ¼ 5.6, 11.5, 17.3, 22.9, 28.2) is added
conversion performance than that of rGC, it can convert more solar (Fig. S11). The results show that the evaporation rate and evapo-
energy to heat and improve evaporation efficiency. ration efficiency of CWO-y%rGC samples fluctuate with the varia-
Due to the injection of Csþ, the carriers in Cs0.32WO3 are bound tion of rGC content, and the difference is smaller compared to that
to the tungsten position and they polarize the surrounding lattice of the rGC-x%CWO samples, which is due to the fixed CWO content
to form small polaritons, which absorb the infrared light when it in CWO-y%rGC samples and the lower degree of CWO influence on
jumps between the W5þ and W6þ positions (Fig. 5a). Under the the restoration of the peconjugate structure of rGC. The highest
combined action of the LSPR effect and the small polaron hopping, values of the evaporation rate and evaporation efficiency of CWO-y
the Cs0.32WO3 nanoparticles produce NIR absorption and photo- %rGC samples reach to 1.77 kg m
2 h
1 and 78.9%, respectively,
thermal conversion performance [56]. According to the Raman which are lower than those of rGC-18.9%CWO. On the contrary, for
spectra analysis in Fig. 4a, it can be inferred that after loading CWO the rGC-x%CWO samples, the oxygen vacancies increase signifi-
nanoparticles, the p-bonds will increase with the restoration of the cantly after CWO compositing with rGC, and the gain effect of rGC
p-conjugated structure in rGC, thus reducing the energy gap be- on CWO is stronger, so the difference of evaporation performance
tween the highest occupied molecular orbital (HOMO) and the caused by the change of CWO content is larger. The results of Figs. 2
lowest unoccupied molecular orbital (LUMO) (Fig. 5b/5c) [57]. As and S11 show that in the cooperation of rGC and CWO, CWO is
a result, rGC can absorb more solar energy, which is consistent with responsible for enhancing the absorbance and photothermal con-
the absorption enhancement in both visible and near-infrared version effect, while rGC provides more support on the structure
bands after loading CWO nanoparticles (Fig. 2i). More incident and thermal conversion process, and both play their respective
photon energy will match the intramolecular electron transition, advantages thus further improving the overall evaporation
meaning that more electrons are excited from HOMO to the LUMO, efficiency.
and relaxed to the ground state via electron-phonon coupling
relaxation (Fig. 5c). In this process, the thermal energy released by
3. Conclusion
the lattice vibrations will increase and the macro-temperature of
the rGC material is raised [58].
In conclusion, we have designed rGC-CWO/CS evaporator,
It is clear from the XPS analysis that rGC-CWO possesses a
verified that the hydrophilic functional groups and excellent
higher carrier density and more oxygen vacancies than CWO, which
wettability of rGC aerogel and CS can activate water molecule,
is beneficial to the enhancement of the small polaron hopping in
which provided a new approach to achieve higher rate by reducing
CWO nanoparticles [56], further improving the NIR absorption.
the evaporation energy consumption. Besides, the characteriza-
Higher NIR absorption and carrier density means stronger LSPR
tions of rGO-CWO aerogels have proved that the appropriate
effect, so the CWO nanoparticles can generate more heat and create
porosity and pore size help to regulate water delivery rate, so that

Fig. 5. Synergistic effect of photothermal conversion process between nano Cs0.32WO3 and rGC aerogel. (A colour version of this figure can be viewed online.)

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G. Li, Q. Wang, J. Wang et al. Carbon 195 (2022) 263e271

the heat can be more concentrated on the evaporation process and Robust graphene@PPS fibrous membrane for harsh environmental oil/water
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Guiqin Li: Conceptualization, Data curation, Writing e original (24) (2020) 9017e9026.
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saving and environmental decontamination functions, Appl. Catal. B Environ.
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The authors declare that they have no known competing [20] W. Guo, C. Guo, N. Zheng, T. Sun, S. Liu, CsxWO3 nanorods coated with
financial interests or personal relationships that could have polyelectrolyte multilayers as a multifunctional nanomaterial for bimodal
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appeared to influence the work reported in this paper.
29 (4) (2017) 1604157.
[21] X. Fang, M. Yao, L. Guo, Y. Xu, W. Zhou, M. Zhuo, C. Shi, L. Liu, L. Wang, X. Li,
Acknowledgements One-step, solventless, and scalable mechanosynthesis of WO3$2h2o ultrathin
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This work was financially supported by the National Natural [22] S. Naseem, C.-M. Wu, T.F. Chala, Photothermal-responsive tungsten bronze/
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