Carbon 149 (2019) 556e563

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

Self-assembly carbon dots for powerful solar water evaporation

Qiao Hou a, 1, Chaorui Xue a, 1, Ning Li a, Huiqi Wang a, Qing Chang a, **, Hantao Liu a,
Jinlong Yang a, b, Shengliang Hu a, *
a
North University of China, School of Energy and Power Engineering & School of Material Science and Engineering, Taiyuan 030051, PR China
b
State Key Laboratory of New Ceramics and Fine Processing, Tsinghua University, Beijing 100084, PR China

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

Article history: Solar-driven water vaporization is considered one of the most sustainable technologies to solve water
Received 27 December 2018 scarcity. However, the advanced design solar absorber system is still required for highly efficient steam
Received in revised form generation. Here we develop a novel system for water evaporation through assembly of carbon dots
19 April 2019
within microchannels of processed wood. Not only is a dual-layer structure including of heat barrier and
Accepted 22 April 2019
Available online 22 April 2019
water transport channel formed, but also the modulation of carbon dot energy structures in favor of
photothermal conversion is realized synchronously. This system exhibits higher water evaporation rate
and energy efficiency for solar to steam generation than other black photothermal sheets (e.g. carbon
Keywords:
Carbon dots
nanotube, graphene, graphene oxide). On the one hand, the constructed size-dependent vaporization
Assembly enthalpy theory shows that the micropores are beneficial to reduce vaporization enthalpy of water. On
Photothermal conversion the other hand, the presented direct evidences for the roles of oxidation functional groups in solar
Solar steam generation thermal evaporation demonstrate that hydroxyl groups can improve solar-to-heat efficiency. Therefore,
tailoring pore sizes and surface functional groups could be an efficient method for solar-to-vapor
systems.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction promoting charge separation and transfer in heterostructures

Fluorescent carbon dots (CDs) with tunable emissions have
inspired intensive research efforts due to outstanding optical
brightness, resistance to photobleaching, excitation/size-
dependent emission property, excellent biocompatibility, low
toxicity, low cost, and abundance of raw materials in nature [1e3].
They have shown potential applications in area of chemical sensors,
bioimaging probes, photocatalysts, light-emitting diode, and so on
[1e7]. More attractive photophysical properties have been found so
far from the composites of CDs and inorganic nanomaterials or
organic molecules rather than single particle of CDs and their as-
sembly [5]. This is because CDs can act as either electron donors or
electron acceptors when coupled with semiconductor materials [8].
The photogenerated electron/hole transfers could occur in hetero-
structures and suppress radiative recombination in CDs (Fig. 1a). So
CDs can be used to improve solar conversion efficiency through
* Corresponding author.
** Corresponding author.
E-mail addresses: changneu@gmail.com (Q. Chang), hsliang@yeah.net (S. Hu).
1
These authors contributed equally to this work.
[1,2,5,9]. Presently, CDs-based heterostructures have exhibited
attractive abilities in pollutant degradation, CO2 reduction, H2
production and organic synthesis [2,4,5].
Without appropriate surface protection, however, the assem-
blies of CDs always create a series of new energy levels at the in-
terfaces of CDs (namely interface states) due to the interactions
between surface groups (e.g., O-related groups). Nonradiative
recombination of photoinduced electrons will thus occur, cause
fluorescence quenching, and release heat (Fig. 1b) [9e12]. Hence,
the proper regulation for CD assemblies will also make it applicable
to converting solar energy into heat as terminal energy for bene-
ficial usage. The light to heat conversion has also gained intensive
research interests in the past decade and found important appli-
cations, including steam generation, water desalination, cancer
therapy, etc.
Water scarcity has become one of the most serious global
challenges of our human being. With respect to this issue, har-
vesting light energy and converting it to heat for assisting water
evaporation is an efficient technological solution to water shortage.
To realize more efficient and economic evaporation, a new concept,
named “Air-Water Interface Solar Heating (AWISH)” has been put
forward and developed because it can restrict heat generation at

https://doi.org/10.1016/j.carbon.2019.04.083
0008-6223/© 2019 Elsevier Ltd. All rights reserved.
 Q. Hou et al. / Carbon 149 (2019) 556e563
Fig. 1. Recombination processes of photogenerated excitons for (a) single carbon dot
and (b) assembly of CDs. Red arrows indicate the flow of excitons in the conduction
band (CB) and valence band (VB). LUMO and HOMO represent lowest unoccupied
molecular orbital and highest occupied molecular orbital, respectively. (A colour
version of this figure can be viewed online.)
the evaporating surface rather than the bulk water, unnecessary
water heating underlying the surface evaporation region can be
efficiently suppressed [13e19]. The light to heat conversion rate
and efficiency will be significantly increased. The key to the effi-
ciency of AWISH process is photothermal materials that are bene-
ficial to exclusively heat up the interfacial water. So far for
photothermal materials, plasmonic metal nanoparticles, composite
particles, carbon-based materials and semiconducting nano-
particles have been exploited and found to perform well in assisting
water evaporation [13e20]. Among them, porous carbon-based
materials (e.g., porous graphene, vertically aligned carbon nano-
tubes) possess advantages of ultra-high broadband solar harvest-
ing, stable physical and chemical properties, low cost and easy
availability, enabling successive research outcomes in the area of
solar water evaporation [13,14,16,18,21e23]. The related reports
have demonstrated that their excellent evaporation performance
could mainly stem from their porous structures, which can confine
light to small volumes by resonant recirculation and facilitate wa-
ter/vapor transportation. However, the challenge remains of how to
optimize the porous structures and what the active sites of pho-
tothermal conversion are for carbon-based nanomaterials.
Compared to two-dimensional graphene and carbon nanotubes
with high thermal conductivity [16], zero-dimensional CDs could
be endowed with low thermal conductivity due to superficial
structure defects and heteroatom groups [1,2]. This is favorable for
heat localization during solar water evaporation process. To the
best of our knowledge, investigation on the usage of CDs for solar
water evaporation has been rarely conducted, and lags far behind
on other carbon materials. Based on above consideration, herein
assembling of CDs within porous basal wood support is developed
and employed for solar water evaporation. We have not only
observed higher energy conversion efficiency and water evapora-
tion rates than other carbon-based nanomaterials, but have also
found that tailoring surface functional groups of CDs and reducing
pore diameters of microchannels are helpful to improve solar-to-
vapor efficiency.
2. Experimental section
2.1. Preparation of CDs
The CDs were prepared via our previously reported method [24],
which is suited for scale-up production with low cost. Typically,
200 mg ultrafine powder of medium temperature coal pitch was
added in mixed solution of 30 mL of formic acid (88%) and 3 mL of
hydrogen peroxide (30%). After reacting for 20 h under continuous
557
stirring, the suspension containing CDs was obtained by centrifu-
gation at 8000 rpm. Finally, CDs powder was collected by removing
the residual liquid in the suspension.
2.2. Wood treatment
Balsa wood was chosen as a support of CDs. The wood needs to
be preprocessed by a similar method reported by Song et al. [25].
The wood was firstly cut into blocks (~5 mm thick) and subse-
quently immersed in 160 mL aqueous solution of containing 20 g
NaOH and 3 g Na2SO3 for cooking. The time was 6 h and tempera-
ture was 100
C. After reaction, wood blocks were taken out and
washed with deionized (DI) water for several times. Subsequently,
the wood blocks were further cooked in 10% H2O2 solution for 1 h
under at 100
C. At last, the treated wood samples were preserved
in a freeze dryer and dried for 12 h.
2.3. Integration of CDs and wood
30 mg of CDs powder was re-dispersed in 1 mL absolute ethanol
via ultrasound treatment. The resultant CDs slurry was uniformly
dropped on the preprocessed balsa wood and then dried in an oven
at 60
C for 20 min. Finally, CDs were assembled on the surface of
wood microchannels. The obtained composite material was named
as CDs@Wood.
2.4. Water evaporation test
The water evaporation performance of samples was measured
by our previous used setup (Schematic shown in Fig. S1) [26]. The
samples were floated on water in a cylinder container that was
surrounded by thermal insulating polystyrene foam. The samples
were irradiated by a solar simulator (CEL-HXUV300, CEAULIGHT,
China) with different optical concentrations on the surface, and the
evaporation experiment were conducted for 60 min at steady-state
condition. The weight of evaporated water was recorded using an
electronic mass balance. The temperatures at the top and bottom
water region were tested using a dual-channel thermocouple for
calculating the temperature difference; surface temperatures were
captured using IR camera.
3. Results and discussion
We have developed a simple, inexpensive, and scalable method
for the preparation of coal-pitch-based CDs. Not only does it pro-
duce CDs with abundant oxygen-containing groups, but it can also
assemble random-sized, widely anisotropic-shaped CDs in a close-
packed (but not aggregated) fashion through gradually removing
the solvent in CD suspension [24]. Fig. 2a shows the photo-
luminescence (PL) spectra of various suspensions with different CD
concentrations at 400 nm excitation. PL emission of CDs presents
apparent redshift with the concentration increase (Inset of Fig. 2a)
and is accompanied by significant reduction of emission intensity.
The PL from CDs suspension with concentration beyond 3 g/L is not
so strong to observe. Nevertheless, the enhancement of CD con-
centration leads to enhanced ultravioletevisible (UVeVis) light
absorption ability over the entire wavelength range investigated
(Fig. S2). The absorption edge is red shifted obviously as CD content
raises. The optical absorption near the band edge follows the
equation: ahv ¼ Aðhv  Eg Þr , in which a, h, v, A and Eg are the ab-
sorption coefficient, Planck constant, light frequency, proportion-
ality constant, and band gap, respectively, and r ¼ 2 for a direct
band gap material and r ¼ 0.5 for an indirect band gap material [4].
Based on UVeVis spectra of Fig. S2, the Tauc plots of converted
(ahv)r versus hv (E) were obtained and shown in Fig. 2b. The optical
558 Q. Hou et al. / Carbon 149 (2019) 556e563

Fig. 2. (a) PL spectra of the suspension with different CDs concentrations excited at 400 nm; (b) The plots of (ahn)2 versus photon energy (hn) for the band gap energies of the
suspension with different CDs concentrations; (c) TEM image of CDs at low concentration, the inset is the HRTEM image of a typical nanoparticle; (d) and (e) TEM and HRTEM
images of CDs at high concentration, respectively; (f) EDS spectrum of CDs; (g) XPS O1s spectrum of CDs, in which three deconvolution peaks are assigned to the relative contents of
eC]O, eCeOH, and eCOOH groups, respectively. (A colour version of this figure can be viewed online.)

band gap can be evaluated by extrapolating the linear section of the
plot to the E axis intercept. The results indicate a decrease in the
optical band gap after CD content increase (Fig. 2b). However, it is
worth noting that this phenomenon of band gap reduction with
concentration increase should be attributed to the interactions
among CDs rather than single CD behavior. High density of CDs in
suspension could promote their contact or aggregation. This situ-
ation probably gives rise to energy transfer between CDs and/or
creates additional energy states at their contacted interfaces [12].
As a result, the light absorption of CD suspension is extended in the
visible light region under high concentration.
TEM characterizations reveal that CDs are dispersive uniformly
in the suspension at low concentration, whereas the dispersal
uniformity decreases at high concentration. Large-sized and
branch-shaped structures appear (Fig. 2c and d). The high resolu-
tion TEM (HRTEM) observations were then carried out to further
explore the structures. The crystalline CDs in dispersed state
possess well-resolved uniform lattice fringes throughout the par-
ticles (Inset of Fig. 2c), while branch-shaped structures display
polycrystalline feature, which is the aggregation of some small and
crystalline domains (Figs. 2e and S3). The size of crystalline do-
mains is also comparable to that of monodispersed CDs. As a result,
it can be concluded that the branch-shaped structures are CD as-
semblies which are built by a number of CDs. With regarding to
chemical composition of CDs, energy dispersive spectroscopy (EDS)
analysis indicates that CDs merely contain C and O elements
(Fig. 2f). Further XPS spectra of O1s shown in Fig. 2g indicate that
there are three components centered at 531.4, 532.6, and 533.5 eV
respectively. According to our previous detailed composition
studies [27], three components are identified to the typical oxygen
functional groups of eC]O, eCOOH and eCeOH on the surface of
CDs. As expected, these superficial O-related groups enable CDs to
form a variety of surface energy traps, and induce additional band
energies after self-assembly.
Apart from low cost, excellent thermal insulation, good hydro-
philicity and machinability, the tree-derived natural wood is one of
the most abundant renewable resources. Because trees require
vertically aligned microchannels to transport water and other
nutrients from the soil during their natural growth, the wood is
endowed with unique anisotropic and porous structure [28,29].
Accordingly, we employed wood as a support of CD assemblies to
realize a solar energy-water nexus. The photos of wood with and
without CD assemblies are shown in Fig. S4. Compared to bare
wood, the color of wood subjected to CD assembling turns into
black, indicating the successful assembling of CDs inside wood.
Fig. 3aec display the top view scanning electron microscope (SEM)
images of the processed wood under different magnifications. The
inherent vertically-aligned and well-defined inner pores are
observed in the wood. The diameters of these pores range from
several to 30 mm. Interestingly, it should be noted that the inner
surface of microchannels is rough and has many small protruber-
ances. This is favorable for the adhesion and assembling of CDs on
the wall of microchannels. For comparison, top view SEM images of
the wood-supported CD assemblies (CDs@Wood) are shown in
Fig. 3def with same magnifications. Clearly, after CD assembling, a
smooth surface structure could be seen due to the filling of small
CDs inside the concave pits of wood. This strongly confirms the
successful assembling of CDs in the wood. Additionally, the repre-
sentative longitudinal SEM images illustrate that CD assemblies
form a new layer on the wall of microchannels (Fig. 3gei). Thus, a
dual-layer structure is produced with CD assemblies as a photo-
thermal layer and wood as a heat barrier layer. Under solar irradi-
ation, such dual-layer structure can facilely create internal hot spot
[16]. When water flows to the hot spot, it evaporates and releases
steam from the microchannels.
The optical absorption spectra of CDs@Wood in contrast with
wood and CDs powder were collected in the wavelength range of
200e2,600 nm. From Fig. 4a, CDs@Wood demonstrates relatively
higher absorption ability than the wood and CDs. Particularly, the
strongest regions (the entire visible region) for optical absorption of
CDs and CDs@Wood coincides with that of the strongest solar ra-
diation, whereas the wood exhibits ultralow optical absorption in
these regions.
The water evaporation rates for CDs@Wood were surveyed by
recording the mass change of water as a function of time, and the
results are compared with pure water and wood under solar
 Q. Hou et al. / Carbon 149 (2019) 556e563
Fig. 3. (aec) Top view SEM images of the used wood under different magnifications; (def) Top view SEM images of CDs@Wood under different magnifications; (gei) Longitudinal
SEM images of CDs@Wood under different magnifications.
illumination of 1 kWm2 (Fig. 4b). The overall mass changes that
represent the weight of evaporated water were recorded once the
surface temperature got to steady state. CDs@Wood shows an
evaporation rate of 2.27 kg m2 h1, which is approximately 4.4 and
3.0 times higher than that of pure water and wood at 1 kW m2
solar illumination, respectively. A higher evaporation rate
(2.5 kg m2 h1) from CDs@Wood can be obtained if the overall
mass changes are recorded when the water temperature is steady.
Accordingly, steam generation with CDs@Wood is more efficient
than pure water and wood. With CDs@Wood and bare wood
floating on water surface, the heat transfer to the non-evaporated
portion of bulk water can be decreased, then enhancing the solar
water evaporation rate. With respect to the accelerated steam
generation for CDs@Wood compared to bare wood, the reason
could be the higher light to heat conversion ability of CDs@Wood
compared to bare wood.
The surface temperature measurement, which is widely used to
evaluate the light to heat conversion efficiency of membrane, was
also conducted. In Fig. S5, After 1 sun illumination for 60 min, the
surface temperature of floating CDs@Wood is 44
C, which is much
higher than that of bulk water (31
C). The temperature increment
for water at the surface of region is shown in Fig. 4c. The temper-
ature rise for pure water system is only 6.1
C, whereas for
CDs@Wood system that reaches about 20.2
C in 1 h irradiation.
This further certifies that the surface water is exclusively heated up
with the assistant of CDs@Wood. The surface temperature incre-
ment for CDs@Wood is also higher than that for bare wood,
559
indicating the higher light to heat conversion ability of CDs@Wood.
The plot of surface temperature versus time signifies different en-
ergy consumption ways. The initial steep region means that the
converted heat energy mainly contributes to surface temperature
rising, while the subsequent plateau region represents the domi-
nating energy consumption by water evaporation through cooling
effect [19]. For pure water system, the surface temperature rises
gradually during solar radiation because the converted energy is
used to heat the bulk water instead of surface water. For the heat
localization and good light to heat conversion ability, the surface
temperature increases sharply at the initial stage with CDs@Wood
floating on the surface. Fig. 4d shows the surface temperature
increment for CDs@Wood under solar illumination of 1.0, 2.0, and
3.0 kW m2, respectively. It can be observed that the surface tem-
perature and steam generation increases with the intensity of solar
irradiation.
In addition to water evaporation rate, the energy conversion
efficiency is also vital parameter for evaluating the possibility of
photothermal materials to generate vapor under ambient condi-
tions. The energy efficiency (h) for solar to steam generation can be
estimated by the following formula [19,20,39],
m_ DHv
h¼ (1)
Copt q0
where m_ (kg m2$h1) is the mass flux, DHv (2260 kJ kg1) is the
vaporization enthalpy of water, Copt is the optical concentration, q0
560 Q. Hou et al. / Carbon 149 (2019) 556e563

2.16 kg m2 h1 (Fig. S7). This indicates the good stability of the
sample of CDs@Wood for recycling.
Under solar illumination of 1 sun, the solar water evaporation
performance between free-standing CDs (namely CDs suspension)
and CDs@Wood was also compared (Fig. 5). In Fig. 5a and b, free
standing CDs exhibit an evaporation rate of 1.09 kg m2 h1 and a
surface temperature increment of 12.7
C, which are much lower
than those of CDs@Wood (2.27 kg m2 h1 and 20.2
C). With the
absence of wood, CDs in the suspension will heat not only the
surface water region but also bottom non-evaporation water re-
gion, so the AWISH process can hardly take place. From Fig. 5b, the
surface temperature gradually rises for CDs suspension with solar
illumination time and no steep region is observed in the plot. This
implies that the more converted energy of free-standing CDs is
used to heat bulk water instead of surface water due to poor
thermal insulating property for heat localization. Apart from ther-
mal insulation function, the porous structure of wood is another
key factors for accelerating solar water evaporation [28,29]. Previ-
ous researches have claimed that the porous structure plays ver-
satile roles in harvesting solar energy for the steam generation
including of light absorber, thermal conversion, pumping water
from bulk water to hot regions, and vapor transport channels
[16,18,19]. However, there is no theoretical guidance for how to
rationally design porous structure yet.
According to classic phase transition theory, the required energy
that pure water is fully vaporized into gas molecules is (See detail
derivation in supporting information) [19],

Fig. 4. (a) UVeVis NIR absorption spectra for wood, CDs powder and CDs@Wood; (b)
DHv ¼ U inter
l þ ðNkB T  pVl Þ (2)
Mass change of water over time under 1 sun illumination (1 kW m2); (c) Temperature
rises of surface for the given samples as a function of time; (d) The effects of optical where Uinter
l (J$mol1) is intermolecular potential of the liquid
concentration on evaporation mass of water and surface temperature rise for water, N (6.02  1023) is the number of water molecules, kB
CDs@Wood; (e) Comparison of steam generation performances of the CDs@Wood and (1.38  1023 J K1) is the Boltzmann constant, T (K) is the tem-
previous reports under 1 sun, the data of R1-R15 from Refs. [20e23,29e39], respec-
perature, p (Pa) is the pressure and Vl (m3$mol1) is the volume of
tively. (A colour version of this figure can be viewed online.)
liquid water. The last term pVl is always neglected because the
volume of liquid water is much smaller than the volume of vapor
(1 kW m2) is the solar irradiation power of 1 sun. for the same amount of molecules. For above thermodynamic
Based on equation (1), the energy efficiency of solar vapor approach, however, the additional pressure arising from surface
generation was calculated and given in Fig. 4e. The energy effi- tension is never taken into account. The surface tension-driven
ciency of CDs@Wood reaches up to 92.5% under 1 sun irradiation. pressure is expressed by the following equation, [28]
Comparing with previous reported carbon-based nanomaterials
such as carbon nanotubes, graphene and/or its oxides
[20e23,29e39], our presented CDs@Wood sample shows the
maximum energy conversion efficiency with a highest evaporation
rate. It is worth mentioning that carbon nanotubeemodified balsa
wood has only an efficiency of 65% at 1 kW cm2 [40], suggesting
that CDs@Wood possesses much better photothermal conversion
performance than carbon nanotubeemodified wood. By contrast,
the energy efficiency for bare wood is merely 13.6% under 1 sun
irradiation, which is far below that for CDs@Wood. This demon-
strates the key role of CDs for light to heat conversion during solar
water evaporation process. After assembling on the wood micro-
channel surface, CDs will interact with each other, and produce
additional band energy. Excellent solar light absorption and non-
irradiative carrier recombination can thus be achieved for better
light to heat conversion performance. The surface architecture can
also be optimized by CDs to accelerate solar water evaporation. To
further clarify it, the contrast experiments for the effects of the
amount of wood-supported CDs on steam generation were per-
formed. The results indicate that the increase of CDs-loading Fig. 5. (a) Mass changes of evaporated water with CDs suspension and CDs@Wood
amount on wood is able to promote evaporation performance of under 1 sun irradiation; (b) Surface temperature increments for CDs suspension and
CDs@Wood as a function of time under 1 sun irradiation; (c) The dependence of water
samples (Fig. S6). What's more, after subjected to solar water
vaporization enthalpy on the pore diameters, the inset is schematic of liquid water in a
evaporation experiment for 4 times under 1 sun radiation, the nanopore; (d) Pore size distributions of wood and CDs@Wood. (A colour version of this
water evaporation rate with CDs@Wood still reached up to figure can be viewed online.)
 Q. Hou et al. / Carbon 149 (2019) 556e563
DP ¼ 4scosq=r
where s is the water vapor-liquid surface tension, q is the contact
angle, r is the pore radius. With equation (3), equation (2) can be
defined as,
DHv ¼ U inter
l þ ½NkB T  ðp þ 4scosq⁄ rÞVl 
From equation (4), it can be seen that the DHv depends on the
pore radius. Thus, the last term could not be considered as zero. For
1 mol water, T ¼ 298 K,s ¼ 0.072 N m2 and q ¼ 0, the relationship
curve between the DHv and pore sizes was obtained and shown in
Fig. 5c. The DHv value of liquid water reduces with the decrease of
pore size. Noticeably, the sharply decreasing region takes place
around 2 nm. When water molecules are confined in 1 nm pore, for
instance, the DHv value will reduce 24% than bulk water. To confirm
this point, the pore sizes existing in wood and CDs@Wood are
carefully examined by BrunauerEmmettTeller (BET) test
(Fig. S8). The BET surface area of CDs@Wood (66.2 m2g-1) is much
higher than that of wood (9.4 m2g-1). Fig. 5d shows that the pore
size distribution in wood (average pore diameter: 14.7 nm) is
strikingly reduced after the CDs assembled on the surface of wood
microchannels (average pore diameter: 1.0 nm). So it can be
concluded that a significant amount of micropores less than 2 nm
are present in the CDs@Wood. However, these micropores could be
Fig. 6. (a) Schematic illustration for selective deactivation of carbonyl, hydroxyl, and carboxylic acid groups on the surface of CDs; (b) IR spectra of CDs, CDs/PH, CDs/BA and CDs/
BrPE; (c) Comparison of vapor generation performances of wood-supported CDs (i.e. CDs@Wood), CDs/PH, CDs/BA and CDs/BrPE under 1 sun irradiation. (A colour version of this
figure can be viewed online.)
561
from the gaps between CDs of assemblies. This case is also
(3) confirmed by the experimental results depicting adsorption phe-
nomena (Fig. S9). The adsorption capacities of wood and
CDs@Wood are very approximate, but the saturated adsorption
time of CDs@Wood is prolonged due to the enhancement of
micropore numbers. Abundant micropores surrounded by CDs not
only promote heat localization, but also minimize vaporization
(4) enthalpy of water due to nanosize-induced additional pressure of
droplets across a curved interface (The inset of Fig. 5c). As a result,
the CDs@Wood is endowed with high-efficiency solar water
evaporation.
Many efforts have been made to prove the roles of O-contained
groups in creating and tuning the band gap in carbon nano-
structures including CDs [2,10,11]. The achieved results have shown
that both the type and amount of oxidation functional groups can
induce the variations of electronic structures as well as catalytic
activities of carbon nanostructures [2,10,11]. The carbonyl groups,
which facilitates the photoinduced charge separation and transfer,
have been identified as the photocatalytic active sites of CDs [27].
For solar thermal water evaporation, however, Yang et al. proposed
that the hydroxyl (OH) and carboxyl (COOH) groups in graphene
absorber could improve solar-to-vapor efficiency due to their
stronger hydrogen bonds with water molecules than carbonyl and
epoxy groups [41]. Unfortunately, they merely offered theoretical
results without direct and convincing chemical evidence. To
562 Q. Hou et al. / Carbon 149 (2019) 556e563
determine the roles of oxidation functional groups in solar thermal
evaporation, the hydroxyl, carbonyl, and carboxylic acid groups on
the surface of CDs were selectively deactivated by surface chemical
reactions [27,42], and then their effects on solar vapor generation
were assessed, respectively.
Fig. 6a shows the schematic illustrations of selective deactiva-
tion reactions of carbonyl, hydroxyl, and carboxylic acid groups
with phenylhydrazine (PH), benzoic anhydride (BA), 2-bromo-1-
phenylethanone (BrPE), respectively. Not only do their reactions be
highly specific, but also own considerable yields under gentle re-
action conditions. For ease of description, the resultant products are
named as CDs/PH, CDs/BA and CDs/BrPE, respectively. The deacti-
vation reactions are confirmed by infrared (IR) spectra. From Fig. 6b,
IR spectra of CDs/BA and CDs/BrPE display the appearances of new
peaks (at 877 and 1627 cm1) associating with phenyl and phenyl
ketone groups. For IR spectrum of CDs/PH, new signals assigned to
the C]N and CeN bonds are observed and the C]O signal intensity
at 1723 cm1 decreases compared to that of CDs. All of these evi-
dences indicate the successful reactions as illustrated in Fig. 6a.
We utilized the same approach to assemble CDs/PH, CDs/BA and
CDs/BrPE in microchannels of the wood, and then surveyed the
evaporation rates of water with them, respectively. As shown in
Fig. 6c, three samples reveal the changes of evaporation mass at 1
sun irradiation for 40 min. Comparing to original CDs@Wood, the
lowest evaporation mass is observed from the sample of CDs/BA,
whereas no apparent change for the sample of CDs/PH. This result
implies that the hydroxyl groups mainly contribute to high solar-
to-vapor efficiency in comparison with the other two types of O-
containing groups. Since oxygen can be removed from different O-
containing groups using hydrazine, the hydrazine has become a
popular deoxygenation agent for reducing graphene oxides [43].
The oxygen contents in CDs are also significantly reduced by hy-
drazine treatment. As shown in Fig. S10, the signals of oxygen-
containing groups for hydrazine-treated CDs are weakened
dramatically comparing with those for original CDs. In consider of
this point, the solar steam generation experiment using hydrazine-
treated CDs was also conducted, and the obtained results are pro-
vided in Fig. 6c. It is clear that the hydrazine-treated CDs display the
lower evaporation mass than the sample of CDs/BA. By this case,
one can deduce that the solar water evaporation rate could be
improved by increasing the content of hydroxyl in CDs or other
carbon materials.
4. Conclusion
In this contribution, we have developed a novel system for
water evaporation through in situ assembly of CDs on the surface of
microchannels of balsa wood. Not only is a duel-layer structure
combining with heat barrier and water transport channel formed,
but also the modulation of carbon dot energy structures in favor of
photothermal conversion is realized. The water evaporation rate
and energy efficiency for solar to steam generation reach up to
2.27 kg m2 h1 and 92.5%, respectively, exceeding other photo-
thermal agents such as carbon nanotube, graphene and/or its oxide.
Taking surface tension-induced pressure into account classic phase
transition theory, the dependence of vaporization enthalpy with
pore diameters is presented and demonstrates that the nanometer-
size holes are beneficial to reduce vaporization enthalpy of water.
Additionally, we offer direct evidences for the roles of oxidation
functional groups in solar thermal evaporation. The solar-to-vapor
efficiency is expected to be improved by enhancing the relative
amount and proportions of hydroxyl groups in CDs. Thereby this
work opens up new ways of designing efficient solar-to-heat
systems.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Nos. U1510125, 51272301, 51502270),
Specialized Research Fund for Sanjin Scholars Program of Shanxi
Province, Program for the Outstanding Innovative Teams of Higher
Learning Institutions of Shanxi, North University of China Fund for
Distinguished Young Scholars, and North University of China Fund
for Scientific Innovation Team.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.carbon.2019.04.083.
References
[1] X. Li, M. Rui, J. Song, Z. Shen, H. Zeng, Carbon and graphene quantum dots for
optoelectronic and energy devices: a review, Adv. Funct. Mater. 25 (2015)
4929e4947.
[2] S.Y. Lim, W. Shen, Z. Gao, Carbon quantum dots and their applications, Chem.
Soc. Rev. 44 (2015) 362e381.
[3] S. Hu, Tuning optical properties and photocatalytic activities of carbon-based
“quantum dots” through their surface groups, Chem. Rec. 16 (2016) 219e230.
[4] J. Liu, Y. Liu, N. Liu, Y. Han, X. Zhang, H. Huang, Y. Lifshitz, S.-T. Lee, J. Zhong,
Z. Kang, Metal-free efficient photocatalyst for stable visible water splitting via
a two-electron pathway, Science 347 (2015) 970e974.
[5] H. Yu, R. Shi, Y. Zhao, G.I.N. Waterhouse, L.-Z. Wu, C.-H. Tung, T. Zhang, Smart
utilization of carbon dots in semiconductor photocatalysis, Adv. Mater. 28
(2016) 9454e9477.
[6] S. Hu, X. Han, Y. Zhou, C. Xue, Q. Chang, J. Yang, Hybrid carbon dot/Ni3S2
architecture supported on nickel foam for effective light collection and con-
version, Chem. Eng. J. 321 (2017) 608e613.
[7] X. Han, Q. Chang, N. Li, H. Wang, J. Yang, S. Hu, In-situ incorporation of carbon
dots into mesoporous nickel boride for regulating photocatalytic activities,
Carbon 137 (2018) 484e492.
[8] X. Wang, L. Cao, F. Lu, M.J. Meziani, H. Li, G. Qi, B. Zhou, B.A. Harruff,
F. Kermarrec, Y.-P. Sun, Photoinduced electron transfers with carbon dots,
Chem. Commun. (2009) 3774e3776.
[9] L. Cao, M.J. Meziani, S. Sahu, Y.-P. Sun, Photoluminescence properties of gra-
phene versus other carbon nanomaterials, Acc. Chem. Res. 46 (2013)
171e180.
[10] L. Bao, C. Liu, Z.-L. Zhang, D.-W. Pang, Photoluminescence-tunable carbon
nanodots: surface-state energy-gap tuning, Adv. Mater. 27 (2015)
1663e1667.
[11] S. Hu, A. Trinchi, P. Atkin, I. Cole, Tunable photoluminescence across the entire
visible spectrum from carbon dots excited by white light, Angew. Chem. Int.
Ed. 54 (2015) 2970e2974.
[12] D. Li, D. Han, S.-N. Qu, L. Liu, P.-T. Jing, D. Zhou, W.-Y. Ji, X.-Y. Wang, T.-
F. Zhang, D.-Z. Shen, Supra-(carbon nanodots) with a strong visible to near-
infrared absorption band and efficient photothermal conversion, Light Sci.
Appl. 5 (2016), e16120.
[13] H. Ghasemi, G. Ni, A.M. Marconnet, J. Loomis, S. Yerci, N. Miljkovic, G. Chen,
Solar steam generation by heat localization, Nat. Commun. 5 (2014) 4449.
[14] X. Li, W. Xu, M. Tang, L. Zhou, B. Zhu, S. Zhu, J. Zhu, Graphene oxide-based
efficient and scalable solar desalination under one sun with a confined 2D
water path, Proc. Natl. Acad. Sci. U. S. A 113 (2016) 13953e13958.
[15] L. Zhou, Y. Tan, D. Ji, B. Zhu, P. Zhang, J. Xu, Q. Gan, Z. Yu, J. Zhu, Self-assembly
of highly efficient, broadband plasmonic absorbers for solar steam generation,
Sci. Adv. 2 (2016), e1501227.
[16] G. Liu, J. Xu, K. Wang, Solar water evaporation by black photothermal sheets,
Nano Energy 41 (2017) 269e284.
[17] P. Yang, K. Liu, Q. Chen, J. Li, J. Duan, G. Xue, Z. Xu, W. Xie, J. Zhou, Solar-driven
simultaneous steam production and electricity generation from salinity, En-
ergy Environ. Sci. 10 (2017) 1923e1927.
[18] M. Gao, L. Zhu, C.K. Peh, G.W. Ho, Solar absorber material and system designs
for photothermal water vaporization towards clean water and energy pro-
duction, Energy Environ. Sci. (2018), https://doi.org/10.1039/C8EE01146J.
[19] F. Zhao, X. Zhou, Y. Shi, X. Qian, M. Alexander, X. Zhao, S. Mendez, R. Yang,
L. Qu, G. Yu, Highly efficient solar vapour generation via hierarchically
nanostructured gels, Nat. Nanotechnol. 13 (2018) 489e495.
[20] P. Zhang, Q. Liao, T. Zhang, H. Cheng, Y. Huang, C. Yang, C. Li, L. Jiang, L. Qu,
High throughput of clean water excluding ions, organic media, and bacteria
from defect-abundant graphene aerogel under sunlight, Nano Energy 46
(2018) 415e422.
[21] Y. Wang, L. Zhang, P. Wang, Self-floating carbon nanotube membrane on
macroporous silica substrate for highly efficient solar-driven interfacial water
evaporation, ACS Sustain. Chem. Eng. 4 (2016) 1223e1230.
[22] P. Zhang, J. Li, L. Lv, Y. Zhao, L. Qu, Vertically aligned graphene sheets mem-
brane for highly efficient solar thermal generation of clean water, ACS Nano
 Q. Hou et al. / Carbon 149 (2019) 556e563
11 (2017) 5087e5093.
[23] Y. Wang, C. Wang, X. Song, S.K. Megarajan, H. Jiang, A facile nanocomposite
strategy to fabricate a rGOeMWCNT photothermal layer for efficient water
evaporation, J. Mater. Chem. 6 (2018) 963e971.
[24] X. Meng, Q. Chang, C. Xue, J. Yang, S. Hu, Full-colour carbon dots: from energy-
efficient synthesis to concentration-dependent photoluminescence proper-
ties, Chem. Commun. 53 (2017) 3074e3077.
[25] J. Song, C. Chen, Z. Yang, Y. Kuang, T. Li, Y. Li, H. Huang, I. Kierzewski, B. Liu,
S. He, T. Gao, S.U. Yuruker, A. Gong, B. Yang, L. Hu, Highly compressible,
anisotropic aerogel with aligned cellulose nanofibers, ACS Nano 12 (2018)
140e147.
[26] C. Xue, S. Hu, Q. Chang, N. Li, Y. Wang, W. Liu, J. Yang, Airewater interface
solar heating using titanium gauze coated with reduced TiO2 nanotubes,
J. Mater. Sci. 53 (2018) 9742e9754.
[27] S. Hu, W. Zhang, Q. Chang, J. Yang, K. Lin, A chemical method for identifying
the photocatalytic active sites on carbon dots, Carbon 103 (2016) 391e393.
[28] C. Jia, Y. Li, Z. Yang, G. Chen, Y. Yao, F. Jiang, Y. Kuang, G. Pastel, H. Xie, B. Yang,
Rich mesostructures derived from natural woods for solar steam generation,
Joule 1 (2017) 588e599.
[29] G. Xue, K. Liu, Q. Chen, P. Yang, J. Li, T. Ding, J. Duan, B. Qi, J. Zhou, Robust and
low-cost flame-treated wood for high-performance solar steam generation,
ACS Appl. Mater. Interfaces 9 (2017) 15052e15057.
[30] G. Wang, Y. Fu, X. Ma, W. Pi, D. Liu, X. Wang, Reusable reduced graphene oxide
based double-layer system modified by polyethylenimine for solar steam
generation, Carbon 114 (2017) 117e124.
[31] V. Kashyap, A. Al-Bayati, S.M. Sajadi, P. Irajizad, S.H. Wang, H. Ghasemi,
A flexible anti-clogging graphite film for scalable solar desalination by heat
localization, J. Mater. Chem. 5 (2017) 15227e15234.
[32] G. Wang, Y. Fu, A. Guo, T. Mei, J. Wang, J. Li, X. Wang, Reduced graphene
oxideepolyurethane nanocomposite foam as a reusable photoreceiver for
efficient solar steam generation, Chem. Mater. 29 (2017) 5629e5635.
[33] Y. Ito, Y. Tanabe, J. Han, T. Fujita, K. Tanigaki, M. Chen, Multifunctional porous
graphene for high-efficiency steam generation by heat localization, Adv.
563
Mater. 27 (2015) 4302e4307.
[34] A. Guo, X. Ming, Y. Fu, G. Wang, X. Wang, Fiber-based, double-sided, reduced
graphene oxide films for efficient solar vapor generation, ACS Appl. Mater.
Interfaces 9 (2017) 29958e29964.
[35] X. Hu, W. Xu, L. Zhou, Y. Tan, Y. Wang, S. Zhu, J. Zhu, Tailoring graphene oxide-
based aerogels for efficient solar steam generation under one sun, Adv. Mater.
29 (2017), 1604031.
[36] Y. Li, T. Gao, Z. Yang, C. Chen, Y. Kuang, J. Song, C. Jia, E.M. Hitz, B. Yang, L. Hu,
Graphene oxide-based evaporator with one-dimensional water transport
enabling high-efficiency solar desalination, Nano Energy 41 (2017) 201e209.
[37] H. Ren, M. Tang, B. Guan, K. Wang, J. Yang, F. Wang, M. Wang, J. Shan, Z. Chen,
D. Wei, H. Peng, Z. Liu, Hierarchical graphene foam for efficient omnidirec-
tional solarethermal energy conversion, Adv. Mater. 29 (2017) 1702590.
[38] N. Xu, X. Hu, W. Xu, X. Li, L. Zhou, S. Zhu, J. Zhu, Mushrooms as efficient solar
steam-generation devices, Adv. Mater. 29 (2017), 1606762.
[39] Y. Yang, R. Zhao, T. Zhang, K. Zhao, P. Xiao, Y. Ma, P.M. Ajayan, G. Shi, Y. Chen,
Graphene-based standalone solar energy converter for water desalination and
purification, ACS Nano 12 (2018) 829e835.
[40] C. Chen, Y. Li, J. Song, Z. Yang, Y. Kuang, E. Hitz, C. Jia, A. Gong, F. Jiang, J.Y. Zhu,
B. Yang, J. Xie, L. Hu, Highly flexible and efficient solar steam generation de-
vice, Adv. Mater. 29 (2017) 1701756.
[41] J. Yang, Y. Pang, W. Huang, S.K. Shaw, J. Schiffbauer, M.A. Pillers, X. Mu, S. Luo,
T. Zhang, Y. Huang, G. Li, S. Ptasinska, M. Lieberman, T. Luo, Functionalized
graphene enables highly efficient solar thermal steam generation, ACS Nano
11 (2017) 5510e5518.
[42] W. Qi, W. Liu, B. Zhang, X. Gu, X. Guo, D. Su, Oxidative dehydrogenation on
nanocarbon: identification and quantification of active sites by chemical
titration, Angew. Chem. Int. Ed. 52 (2013) 14224e14228.
[43] S. Stankovich, D.A. Dikin, R.D. Piner, K.A. Kohlhaas, A. Kleinhammes, Y. Jia,
Y. Wu, S.T. Nguyen, R.S. Ruoff, Synthesis of graphene-based nanosheets via
chemical reduction of exfoliated graphite oxide, Carbon 45 (2007)
1558e1565.