Energy 227 (2021) 120483

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Energy
journal homepage: www.elsevier.com/locate/energy

The MXene/water nanofluids with high stability and photo-thermal

conversion for direct absorption solar collectors: A comparative study
Hao Wang, Xiaoke Li*, Boqiu Luo, Ke Wei, Guangyong Zeng**
College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu, 610059, China

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

Article history: The efficient utilization of solar energy is a prominent problem in the field of energy in today’s society.
Received 21 November 2020 The judicious combination of nanofluid and direct absorption solar collector (DASC) is one of the effective
Received in revised form ways to solve this problem. Two-dimensional nanomaterials have attracted significant research atten-
6 March 2021
tions because of their unique optical and thermophysical properties. In this paper, two-dimensional
Accepted 19 March 2021
MXene nanosheets were prepared by in-situ etching. Then different concentrations (5, 10, 20, 40,
Available online 31 March 2021
60 ppm, respectively) of MXene and graphene nanofluids were obtained by two-step method. The optical
and thermal conductivity of the two nanofluids were further tested. The MXene nanofluids exhibited
Keywords:
MXene
advanced optical properties due to the LSPR effect of MXene nanosheets, but the graphene nanofluids
Nanofluids had higher thermal conductivity. When the concentration was 20 ppm, the photothermal conversion
Stability efficiency of MXene nanofluids reached a maximum of 63.35%, which was 4.34% higher than that of
Thermal conductivity graphene nanofluids. Finally, through the analysis of local conversion efficiency, the working conditions
Photothermal conversion of DASC were further optimized.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction
With the continuous progress of industrial civilization, the de-
mand for energy has reached an unprecedented height. Nowadays,
fossil energy, a non-renewable energy source, is the protagonist of
energy supply, but the environmental problems caused by fossil
fuel use cannot be ignored. Finding and in-depth study of clean and
sustainable energy has become the focus of people in resolving
energy conflicts. As an important source of energy for the fore-
seeable future, the efficient utilization of solar energy is one of the
momentous directions of current research. Photovoltaic [1,2],
photothermal [3,4], photochemical [5] and photobiological [6]
conversion are the main methods of solar energy utilization.
Among them, the solar photothermal utilization is currently the
most mature form of solar energy utilization due to its high energy
conversion efficiency, wide application range and low cost [7e9].
There are two strategies for using solar thermal energy directly:
surface absorption solar collector (SASC) [10] and direct absorption
* Corresponding author. Postal address: No.1, Dongsan Road, Erxianqiao, Chen-
ghua District, Chengdu, 610059, PR China.
** Corresponding author. Postal address: No.1, Dongsan Road, Erxianqiao, Chen-
ghua District, Chengdu, 610059, PR China.
E-mail addresses: xiaokeli319@126.com (X. Li), wuwu5125@163.com (G. Zeng).
solar collector (DASC) [11,12], which are shown in Fig. 1(a) and (b).
Considering the large heat loss of solar collectors based on surface
absorption, DASCs are the main direction of photothermal con-
version. However, traditional absorbing fluids (i.e. water, glycol, oil,
etc.) have high transmittance in the visible and near-infrared bands.
Hence the light energy cannot be “trapped” in the fluids, resulting
in low efficiency of photo-thermal conversion (PTC) [13e15].
Fortunately, the emergence of nanofluids, a fluid originally
designed to solve the low heat transfer limitation [16], provides a
solution to the problem of low photothermal efficiency of DASCs.
Combining nanoparticles with traditional working fluids could
significantly improve the PTC efficiency of DASCs. At the same time,
the volumetric absorption of nanofluids further enhances the ab-
sorption of solar energy [17e19], as shown in Fig. 1(c). In recent
years, the nanofluids based DASCs systems have fascinated many
researchers. Mehrali et al. [20] studied the graphene/silver nano-
fluids of DASCs. It was found that the increase in the content of
silver nanoparticles significantly enhanced the volume absorption
effect of solar energy. Furthermore, silver nanoparticles have local
surface plasmon resonance (LSPR), resulting in an up to 77%
enhancement of photothermal conversion efficiency. Xuan et al.
[21] combined TiN nanoparticles with LSPR effect in the visible
band and Fe3O4 nanoparticles with strong absorption in the near
infrared region to prepare magnetic nanofluids, which can not only

https://doi.org/10.1016/j.energy.2021.120483
0360-5442/© 2021 Elsevier Ltd. All rights reserved.
H. Wang, X. Li, B. Luo et al.
Fig. 1. Schematic diagrams of (a) SASC, (b) DASC, (c) nanofluids-based DASC and (d) MXene nanosheets absorb solar radiation.
absorb solar energy in broadband, but also regulate the photo-
thermal properties by the change of magnetic field. Finally, the
photothermal properties of the prepared nanofluids were evalu-
ated by volume solar energy conversion system. Li et al. [22] pre-
pared the hybrid nanofluid containing SiC nanoparticles and
MWCNTs and applied it to DASC systems. The results revealed that
the PTC efficiency of 1 wt% nanofluid was as high as 97.3%, which
was 48.6% higher than that of the base fluid. According to the above
analysis, it is obvious that the selection of nanomaterials plays a
vital role in the performance of solar photothermal system.
2
Energy 227 (2021) 120483
The investigation of two-dimensional nanomaterials began to
rise when Novoselov and Geim obtained graphene for the first time
by mechanical exfoliation [23]. Due to its unique two-dimensional
planar structure and excellent optical, thermal, electrical and me-
chanical properties, it has huge application potential in many fields
[24e26]. After continuous exploration, the properties and appli-
cations of nanofluids based on graphene and its composite mate-
rials have been widely reported [27e29]. From the perspective of
photothermal utilization, the extremely high thermal conductivity
and spectral absorption characteristics of graphene seem to be
H. Wang, X. Li, B. Luo et al.
perfect. However, the shortcomings of graphene and its derivatives,
such as toxicity, high price, and environmental pollution, cannot be
ignored [30e32], which motivates people to develop new two-
dimensional materials.
Finally, in 2011, Gogotsi and Barsoum et al. jointly discovered a
new type of graphene-like transition metal two-dimensional ma-
terial [33]. As a result, MXene enters people’s field of vision. MXene
is generally obtained by selectively etching the A atoms of MAX
phase (a layered ternary metal carbide, nitride and carbonitride,
where M ¼ transition metal, A ¼ III or IV main group element,
X ¼ carbon or nitrogen element). Compared with graphene, the
MXene not only succeeds the outstanding properties of traditional
two-dimensional nanomaterials, but also has large interlayer
spacing, good biocompatibility, high conductivity and hydrophi-
licity [34]. Therefore, it has a wide application prospect in the fields
of supercapacitors [35], energy storage [36], sensors [37], lubricants
[38] and membrane separation [39]. With the deepening of the
research on MXene, the performance of nanofluids containing
MXene has also attracted the attention of researchers. Bing et al.
[40] compared the thermal conductivity and viscosity of monolayer
and multilayer Ti3C2Tx glycol-based nanofluids. It was found that
the monolayer MXene nanofluids exhibited excellent thermal
conductivity. At 25  C, the thermal conductivity of 5 vol% mono-
layer MXene nanofluids is 64.9% higher than that of ethylene glycol.
In addition, the viscosity of multi-layer MXene was significantly
lower than that of single layer due to the self-lubricating property.
Ananthakumar et al. [41] used MXene nanofluids prepared by MAX
phase (Ti3SiC2) as coolants. The research showed that the thermal
conductivity of the fluid was increased by 45% when the particle
load was 0.25 vol% at 323 K. Meanwhile, it was found that at
303e333 K, the relative viscosity of all MXene nanofluids was less
than 1, in which at 303 K and the shear rate of 200 s1, the relative
viscosity of 0.2 vol% MXene nanofluids was 30% lower than that of
the base fluid (propylene glycol), indicating that the unique rheo-
logical behavior of MXene nanofluids. Aslfattahi et al. [42] applied
MXene (Ti3C2)/silicone oil nanofluids to centralized photovoltaic
collectors and found that the thermal conductivity was improved
by 64% compared with pure silicone oil. However, the MXene
nanofluids reported in the above literatures all used non-aqueous
base fluids, and currently there are relatively few studies on
water-based MXene nanofluids. Abdelrazik et al. [43] prepared
water/Ti3C2 nanofluids with different surfactants (CTAB and SDBS)
and applied them to the spectral frequency division of PV/T sys-
tems. It is well known that although MXene has good hydrophilic
properties, the obtained MXene is easily oxidized and degraded in
water, which makes the properties of MXene nanosheets lost. In
fact, water is the most commonly used working fluid in cryogenic
DASC systems because of its low price and wide sources. Therefore,
it is necessary to solve the stability of MXene in water for the
application of MXene nanofluids in DASC. Commonly used methods
to enhance the anti-oxidation ability of MXene mainly rely on low
temperature or creating an oxygen-free environment. Recent
studies have shown that the addition of antioxidants [44] or
coupling agents [45] and freezing methods [46] can effectively
prevent the oxidation of MXene in aqueous solution. Hence, the
sodium citrate as antioxidant and dispersant was used in this study
Table 1
Basic information of nanopowders.
Materiala Purity(%) Density(g/cm3) Layers
MAX 98 4.2 e Ti, Al, C
Graphene >99.5 0.23 <20
a
Data provided by the supplier.
3
Energy 227 (2021) 120483
to solve the mentioned problem. On the other hand, different from
other two-dimensional nanomaterials, it has been proved that
MXene (Ti3C2Tx) also exhibits the effect of LSPR in the optical field
[47,48]. These promising properties coupled with high thermal
conductivity make Ti3C2Tx as a suitable candidate for photothermal
applications.
In this research, multilayer MXene was prepared by in-situ
etching. Water-based nanofluids with different concentrations (5,
10, 20, 40, 60 ppm, respectively) of Ti3C2Tx and graphene were
prepared respectively by two-step method using sodium citrate as
antioxidant and dispersant. Then, the stability, thermal conduc-
tivity and optical properties of nanofluids were discussed
emphatically. Finally, the photothermal conversion experiments
were conducted with nanofluids to evaluate the application po-
tential of the two kinds of nanofluids in DASCs. We believe this
work will fill the experimental gaps in the field of water-based
Ti3C2Tx nanofluids. The photothermal conversion experiments
will provide an optimization scheme and analysis strategy for
DASCs containing two-dimensional nanomaterials.
2. Materials and methods
2.1. Materials and reagents
MAX phase (Ti3AlC2, 400 mesh, 98%) powders was obtained
from 11 Technology Co., Ltd (Jilin, China). Graphene nanosheets
were provided by Chengdu Institute of Organic Chemistry
(Chengdu, China). The basic information of nanopowders is listed in
Table 1. Analytical grade hydrochloric acid (HCl) and sodium citrate
were purchased from Chronchem Chemical Reagent Factory
(Chengdu, China). Lithium fluoride (99.9%) was provided by
Aladdin (Shanghai, China).
2.2. Synthesis of MXene
MXene nanosheets(Ti3C2Tx) was synthesized by in-situ etching
of Ti3AlC2 (MAX phase) with HCl/LiF etching agent [49]. Half a gram
of LiF was added to 15 mL of 12 M HCl and stirred for half an hour to
fully dissolve it. Then half a gram of Ti3AlC2 powder were slowly
added (adding process lasted 15 min) and magnetically stirred at
30  C for 20 h. The resulting sludge was diluted with deionized
water until pH reached 6. So as to obtain delaminated Ti3C2Tx, the
product was dissolved in 200 mL of DI water, and the solution was
sonicated for 4 h under a nitrogen atmosphere. The mixed solution
was centrifuged at 10,000 rpm for 30 min, and then removed the
supernatant. Finally, the centrifuged solution was dried overnight
in a vacuum oven to get the final Ti3C2Tx powder. The schematic
diagram of the preparation process of Ti3C2Tx is shown in Fig. 2.
2.3. Preparation of nanofluids
Considering the easy oxidation of MXene in water and the weak
hydrophilicity of graphene, the sodium citrate as an antioxidant
and anionic surfactant, was used to prepare nanofluids. Ti3C2Tx
nanoparticles of different mass concentrations (5, 10, 20, 40,
60 ppm, respectively) were dispersed in deionized aqueous
Element Particle size Appearance
400 mesh Black powder
C 5e10 mm Grey brown powder
H. Wang, X. Li, B. Luo et al. Energy 227 (2021) 120483

Fig. 2. The preparation process of multilayer Ti3C2Tx.

solution with the concentration of 2000 ppm sodium citrate, and 2.5. Photo-thermal conversion experiment
the nanofluids were prepared by ultrasonic for 20 min. Then, the
same concentration of graphene nanofluids were prepared by the The schematic diagram of the photothermal conversion device
same method. designed for this experiment is shown in Fig. 3(a). The nanofluids
were packed in a special quartz beaker with a diameter of 4 cm and
a height of 6 cm. The beaker was surrounded by a polystyrene
2.4. Characterization and performance testing
insulation layer with a thermal conductivity of about 0.03 W/(m$K),
and a quartz glass plate was covered on the beaker. These opera-
The thermal conductivity of nanofluids was measured by KD-
tions were mainly used to prevent heat loss during the experiment.
2pro (Decagon Devices, Inc., USA) thermal characteristic analyzer
The CEL-HXUV300 xenon lamp light source (Zhongjiao Jinyuan
(the detailed process of thermal conductivity measurement was
Science Co., Ltd. Beijing, China) was used as the sunshine simulator,
given in the Supporting Information).
which matched with the standard AM1.5 spectrum well. The inci-
The morphology of MAX, MXene and graphene were obtained
dent radiation flux was accurately measured by a solar radiometer
by using SU8220 scanning electron microscope (SEM, HITACHI,
(HD2302, Italy Delta-Ohm). To evaluate the temperature distribu-
UHR). The microstructure of MXene was further characterized by
tion of the samples, four thermocouples (K-type) were installed at
dimension icon atomic force microscopy (AFM, Bruker instrument)
different heights of the beaker (h ¼ 0.5, 1.5,2.5,3.5, h represents the
and transmission electron microscopy (TEM, Libra 200 FE, ZEISS).
distance from the installation position of the thermocouple to the
The spectrophotometer (UVeViseNIR, Alpha-1860) was utilized to
top of the beaker. mi represents the mass of the fluid evenly divided
get the optical properties (190e1100 nm) and stability
according to the thermocouple.), as shown in Fig. 3(b). The
(400e900 nm) of two kinds of nanofluids.

Fig. 3. (a) Schematic diagram of photothermal conversion test system; (b) Distribution of thermocouple and working fluid.

4
H. Wang, X. Li, B. Luo et al. Energy 227 (2021) 120483

temperature data was transmitted to the computer through the 3. Results and discussions
recording unit (Omega-TC08). Each sample was measured at an
interval of 10 s for a total of 2500 s. 3.1. Characterization

The morphologies of MAX phase, MXene and graphene nano-

materials were characterized and analyzed by SEM. Fig. 4(a) shows
2.6. Performance indices and error analysis that MAX presents a layered and dense massive structure. The
MXene obtained by etching has a lamellar structure (see Fig. 4(b)).
Extinction coefficient is an important parameter to detect the It can be found from Fig. 4(c) that the particle size of graphene
optical absorption performance of nanomaterials. It was obtained nanosheets is about 5 mm. Fig. 4(d) shows the morphology of the
by formula (1) based on Lambert-Beer law [50]: graphene. Structurally, both graphene and MXene have two-
dimensional layered structures.
TðlÞ ¼ expðaðlÞdÞ (1) The microstructure of Ti3C2Tx was further characterized by TEM
and AFM. The TEM morphology of MXene is clearly shown in
whereaðlÞandTðlÞrepresent the extinction coefficient and trans- Fig. 5(a). It shows the structure of MXene clearly, which reveals that
mittance of nanofluids, respectively. d means the optical path MXene is a kind of graphene-like 2D nanomaterial with wrinkled
length. structure. In addition, HRTEM image presents that the thickness of
The theoretical absorption of spectral irradiance by nanofluids the etched single-layer nanosheets is about 1 nm from Fig. 5(b).
could be obtained by formula (2) [51]: AFM (shown in Fig. 5(c)) indicates that the thickness of MXene is
about 5 nm. To sum up, the prepared MXene nanosheet has about 5
IA ðlÞ ¼ IAM1:5 ½1  eaðlÞx  (2) layers.
The XRD patterns of MAX phase and MXene are displayed in
where IAM1:5 ðlÞ represents the incident solar irradiation in a certain Fig. 5(d). Macroscopically, the diffraction peak of MAX phase pre-
wavelength range (ASTM AM1.5 global). cursor is high and sharp, indicating that it has high quality.
The solar weighted absorption fraction was calculated by Compared with MAX phase, the etched MXene does not have any
formula (3) [52]. distinct characteristic peak (104), meaning that Al has been
removed successfully. At the same time, the intensity of the (002)
ð
diffraction peak of MXene decreases significantly and shifts to a
IAM1:5 ½1  eaðlÞx dl
smaller angle. According to the Bragg equation, it is shown that the
FðxÞ ¼ ð (3)
interlayer spacing of the etched MXene becomes larger than MAX
IAM1:5 ðlÞdl
[40]. Han et al. [53] proposed that the number of MXene layers was
related to the angle corresponding to the (002) diffraction peak,
The solar weighted absorption fraction represents the propor-
and the smaller the number of layers, the smaller the peak would
tion of solar energy absorbed at a given penetration distance x.
move to a smaller angle. In summary, MXene nanosheets were
The energy absorbed by the nanofluids through PTC could be
successfully prepared.
obtained by formula (4):
3.2. Stability of nanofluids
X
z X
n
QA ¼ cnf ðmi DTi Þ (4)
1 i¼1 In this study, the stability of two kinds of nanofluids was eval-
uated and compared by visual method and spectrophotometer.
where mi is the mass, cnf represents the specific heat capacity and Fig. 6(a) and (b) are comparative diagrams of MXene and graphene
DTi indicates temperature change of nanofluids, respectively. nanofluids on different time (room temperature ¼ 23  C). The
Formula (5) was used to calculate the photothermal conversion comparison results showed that the color of MXene nanofluid had
efficiency of nanofluids. no obvious change after standing for 2 weeks and there was no
precipitation at the bottom of the bottle. It indicated that the
QA addition of sodium citrate significantly improved the oxidation
hTC ¼ ð t (5) resistance and stability of MXene nanofluids [54]. In contrast, the
GAdt graphene nanofluid had obvious precipitation. Through the com-
0
parison of transmittance, the stability of the two fluids was further
where G is solar irradiance, A is the superficial area of the beaker clearly verified (see Fig. 7.). The transmittance changes of MXene
mouth, t represents the illumination time. nanofluids at different concentrations were less than 5%, while the
The experimental error of photothermal conversion experiment transmittance changes of graphene were more than 10% when the
is caused by various measurement errors, including the mass m of concentration of graphene was higher than 5 ppm. MXene
the nanofluid, the temperature T of the thermocouple, the optical exhibited better stability than graphene, which was mainly
depth l and the radiation intensity I. Therefore, the relative error Eh contributed to the extremely strong hydrophilicity of many hy-
of photothermal conversion efficiency is obtained from the Eq. (6) drophilic groups on the surface of Ti3C2Tx. At the same time, the
[15]: experimental results once again confirmed the effect of particle
concentration on the stability of nanofluids, that was, the higher
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi the concentration, the less conducive to fluid stability [55]. Finally,
u 4  2    2  2
uX dTi dm 2 dl dI the above conclusions were further verified by analyzing the Zeta
Eh ¼ t þ þ þ (6)
T i m l I potential of the two nanofluids (see Supporting Information).
i¼1

In this investigation, the maximum uncertainty of photothermal 3.3. Thermal conductivity

conversion experiment is 3.1326%, therefore the experimental re-
sults are reliable. In the direct absorption collector, thermal conductivity is an
5
H. Wang, X. Li, B. Luo et al.
Fig. 4. SEM images of (a) MAX phase (Ti3AlC2), (b)Ti3C2Tx and (c) graphene.
important index to measure the heat transfer rate of working fluid.
The two-dimensional materials have considerable aspect ratio and
specific surface area, which greatly reduces the contact thermal
resistance between the nanosheet and the basic fluid [56]. There-
fore, the thermal conductivity of the heat transfer working fluid can
be significantly improved. As far as the author knows, there is no
assessment of the thermal conductivity of MXene/water nano-
fluids. Fig. 8(a) depicts the thermal conductivity of the two nano-
fluids as a function of particle concentrations at 45  C. The
enhancement of thermal conductivityhT was calculated by formula
(7):
knf  kb
hT ¼  100
kb
where knf and kb represent the thermal conductivity of nanofluids
and water, respectively. Obviously, the thermal conductivity values
of graphene nanofluids are significantly higher than that of MXene
nanofluids. The thermal conductivity of the two nanofluids shows a
tendency to increase with the increase of concentration. At the
highest concentration, the thermal conductivity of graphene
nanofluid is increased by 15.5% compared with water, while MXene
nanofluid is only increased by 9.6%. This may be related to the
Energy 227 (2021) 120483
nature of MXene and the structural defects after chemical etching.
Bing et al. [40] obtained similar conclusions on ethylene glycol
based graphene and multilayer MXene nanofluids, respectively.
Temperature is an important factor that must be discussed for
changes in thermal conductivity. The temperature dependence of
thermal conductivity of two nanofluids (both 60 ppm) is compared
in Fig. 8(b). Temperature has a significant positive effect on the
thermal conductivity of both nanofluids. The Brownian motion of
the nanosheet in the base fluid is considered to be the main reason
of this phenomenon [57]. The thermal conductivity of graphene is
5.5% higher than that of MXene at 50  C. It is worth noting that the
results of Bing et al. [40] showed that the thermal conductivity of
ethylene glycol-based MXene nanofluids did not change with
(7) temperature. This phenomenon has been attributed to the high
viscosity characteristics of the base fluid, which further confirms
the importance of the selection of the base fluid to the application.
From the comparison in Fig. 9, it can be clearly seen that the gap
between graphene and MXene nanofluids gradually expands with
the increase of temperature and concentration. In the process of
photothermal conversion, the working fluid with higher thermal
conductivity will be more conducive to rapid heat transfer, which
will help to reduce the heat loss.
6
H. Wang, X. Li, B. Luo et al.
Fig. 5. (a) TEM, (b) HRTEM and (c) AFM of MXene. (d) The XRD patterns of Ti3AlC2 and Ti3C2Tx.
3.4. Optical properties of nanofluids
The research of the optical properties of materials plays an
important guiding role in optimizing the photothermal application
of solar energy. There are two ways to fundamentally improve the
optical properties of nanofluids, including increasing the optical
absorption intensity of nanomaterials and broadening the wave-
length range of the absorption spectrum of nanofluids. Considering
that more than 80% of the energy of solar radiation is concentrated
7
Energy 227 (2021) 120483
in 200e1100 nm, this work focused on the optical properties of the
two studied nanofluids in this wavelength range. Fig. 10 compares
the transmittance of the two nanofluids. Obviously, MXene nano-
fluids exhibits more excellent spectral absorption characteristics at
the same concentration. At the highest concentration (60 ppm), the
transmittance of MXene nanofluids is close to 0% in the full band,
while graphene nanofluids still has a spectral transmittance of
more than 10%. The main reason for this phenomenon is that when
the concentration of nanosheets increased, the scattering effect of
H. Wang, X. Li, B. Luo et al. Energy 227 (2021) 120483

Fig. 6. The prepared nanofluids (a) MXene (b) graphene (0, 5, 10, 20, 40, 60 ppm from left to right).

Fig. 7. The transmittance of nanofluids just prepared (solid line) and standing for two weeks (dotted line) (a) MXene (b) graphene.

Fig. 8. (a) Thermal conductivity ratio vs. concentrations for MXene and graphene nanofluids at 45  C. (b) Thermal conductivity of MXene and graphene nanofluids at a concen-
tration of 60 ppm from 25  C to 50  C.

the top layer of the fluid increases significantly. At the same time, dimensional materials, the scattering effect is enhanced, resulting
according to Mie theory [58], due to the larger size of two- in a decrease in transmittance. However, MXene nanomaterials

8
H. Wang, X. Li, B. Luo et al. Energy 227 (2021) 120483

Fig. 9. Thermal conductivity by MXene (blue) and graphene (red) nanofluids with different concentrations and temperature. (For interpretation of the references to color in this
figure legend, the reader is referred to the Web version of this article.)

Fig. 10. Transmittance of (a) MXene, (b) graphene nanofluids with different mass concentration.

have extremely strong electromagnetic wave absorption property.
Shahzad et al. [59] investigated the electromagnetic shielding effect
of MXene nanomaterials. As shown in Fig. 1(d), it is found that the
electromagnetic waves can be continuously reflected between
layers through the lattice structure of MXene nanosheets, and
finally be absorbed. These phenomena prove that MXene two-
dimensional materials can absorb solar energy more effectively in
wide band.
In addition to the excellent performance in the ultraviolet and
visible region, the unique optical properties of MXene nanofluids in
the near-infrared region are also remarkable. As shown in Fig. 10,
the transmittancy of Ti3C2Tx nanofluids exhibits an obvious ab-
sorption valley in the band of 700e900 nm. This prominent optical
absorption phenomenon is attributed to the LSPR [60]. The simple
harmonic oscillation of free electron caused by plasmon with
incident radiation can produce high light absorption and extinction
cross-sectional area, which will be beneficial for nanofluids to
absorb solar energy directly [61]. This is consistent with the
conclusion of the research conducted by Lin et al. [62] They also
found that Ti3C2Tx nanosheets have a strong absorption peak in the
near-infrared region (750e850 nm). However, the other two-
dimensional materials do not have the similar properties.

9
H. Wang, X. Li, B. Luo et al.
Fig. 11. Extinction coefficient of (a) MXene (b) graphene nanofluids.
Fig. 11 shows the extinction coefficients of MXene and graphene
nanofluids with different concentrations. Concentration is one of
the main factors affecting the extinction coefficient, and Ti3C2Tx
nanofluids exhibits significant absorption characteristics in the
whole wavelength range. The extinction coefficient of 60 ppm
Ti3C2Tx nanofluids is about 50% higher than that of graphene
nanofluids. In the near infrared band (700 nme900 nm), the sig-
nificant extinction peak of MXene nanofluids further verifies the
ideal LSPR effect of MXene for broad spectrum absorption. Unfor-
tunately, graphene nanofluids does not show similar properties.
Therefore, it can be concluded that the MXene nanofluids with high
extinction coefficient and LSPR effect can achieve the required
spectral absorption effect even under lower concentration
conditions.
The curves in Fig. 12(a) and (b) represent the theoretical ab-
sorption of spectral irradiance by Ti3C2Tx and graphene nanofluids,
respectively. The area under the curve represents the energy
absorbed by the nanofluids. The solar energy absorption capacity of
40 ppm MXene nanofluids is even stronger than that of 60 ppm
graphene, and the Ti3C2Tx nanofluid of 60 ppm theoretically ab-
sorbs 97.66% of solar energy. It is worth noting that the energy
absorption is obviously affected by the concentration of nano-
materials. But, the efficient solar energy absorption of nanofluids
will encounter a bottleneck when the concentration reaches a
certain level. In other words, Ti3C2Tx nanofluid with 60 ppm has no
significant improvement in solar energy absorption compared to
Fig. 12. Spectral irradiance by (a) MXene (b) graphene nanofluids (penetration distance ¼ 1 cm).
10
Energy 227 (2021) 120483
40 ppm. Therefore, it is necessary to explore the best combination
of material properties and concentration in the process of light
energy absorption. Optimistically, the MXene nanofluids with low
concentrations can achieve a high spectral solar absorption, which
is very conducive to the application of DASCs.
In addition, determining the optimal fluid depth in the DASCs is
an inevitable problem. Using nanofluid as the light absorption
medium of the collector can significantly reduce the fluid depth.
However, Zhang et al. [63] found that too small fluid depth would
not be able to convert and store enough incident energy. At the
same time, when the fluid depth exceeds 4 times the penetration
depth of the nanofluid, the efficiency of the collector will not be
improved [61]. The above conclusions indicate that there is an
optimal fluid depth for DASCs to achieve maximum heat collection
efficiency. The comparison of the solar weighted absorption frac-
tion of the two fluids is shown in Fig. 13. The F(x) increases with the
penetration distance for both nanofluids. Meanwhile, the particle
concentration put an obvious effect on the solar weighted ab-
sorption fraction. However, the ability of Ti3C2Tx nanofluids to
capture solar energy is significantly better than graphene nano-
fluids. Specifically, when the penetration distance is 1 cm, the solar
energy weighted absorption fraction of graphene nanofluids of
60 ppm is 0.817. And the value is 0.977 for MXene nanofluids, which
is 19.6% higher than that of graphene nanofluids. In addition, the
Ti3C2Tx nanofluids of 60 ppm could achieve full absorption at only
2 cm penetration distance. This means that only a very thin
H. Wang, X. Li, B. Luo et al.
Fig. 13. The relationship between solar weighted absorption fraction and penetration distance for (a) MXene (b) graphene nanofluids.
thickness of MXene nanofluids is needed to achieve efficient pho-
tothermal absorption in DASCs applications.
3.5. Photo-thermal conversion
3.5.1. Temperature distributions
In the photothermal conversion experiment, the change of
temperature is the most direct embodiment to measure the pho-
tothermal conversion performance of nanofluids. The time
dependence of the temperature difference (TD) of two nanofluids
could be found in Fig. S3. The TD of all fluids increases with the
illumination time, and the maximum TD increases significantly
with the mass concentration. The maximum TDs on the top of
container for water, Ti3C2Tx nanofluids and graphene nanofluids
are 13.2  C, 21.9  C and 20.4  C after an irradiation time of 2500 s,
respectively. In addition, the temperature difference between water
and two nanofluids at different heights is also significant. For
instance, the maximum TD between the top and the bottom of
collector for water, graphene nanofluid and Ti3C2Tx nanofluid is
4.2  C, 11.5  C and 13.2  C, respectively.
The temperature distributions inside the working fluids of DASC
after 2500 s of illumination are shown in Fig. 14. From the overall
trend, the temperature difference distribution trends of the two
nanofluids are consistent. However, a large temperature difference
between the two nanofluids (10 ppm) in the deeper part of the
Fig. 14. Temperature distribution curves at different heights and concentrations for the (a) MXene (b) graphene nanofluids after irradiation time of 2500 s (The solid line does not
represent data, but only serves as a trend indicator.).
11
Energy 227 (2021) 120483
collector is observed, which is related to their relatively high
transmittance. This means that more nanoparticles can participate
in the process of photothermal conversion, reflecting the charac-
teristics of volume absorption of nanofluids. However, as the con-
centration increases, the larger temperature difference distribution
begins to shift to a shallower area, and the change trend of the
internal temperature difference in the fluid gradually increases. The
larger temperature difference is mainly concentrated in the depth
of 1 cm, especially for the MXene nanofluids, which own extreme
strong surface absorption characteristics. The transmittance of
nanofluids plays a key role here. As mentioned earlier, when the
optical path is 1 cm, the Ti3C2Tx nanofluid of 60 ppm has almost no
light transmission, but the transmittance of graphene nanofluid is
still higher than 10%. Therefore, one can conclude that the Ti3C2Tx is
an excellent photothermal conversion material.
3.5.2. Photo-thermal conversion efficiency
The calculation of the photothermal efficiency in this study is
based on the following two assumptions: (1) The heat loss at the
bottom and side walls of the collector is negligible; (2) Considering
the low concentration of nanofluid (ppm), the density and specific
heat capacity are approximately equal to those of the base fluid.
Fig. 15 shows the energy absorption of nanofluids after 2500 s of
light irradiation. During this period, the simulated light source
provided a total of about 4700 J of energy, while water could only
H. Wang, X. Li, B. Luo et al.
Fig. 15. (a) Energy absorption and (b) photothermal conversion efficiency of MXene and graphene nanofluids (illumination of 2500 s).
absorb 1700 J of energy. As a comparison, the energy absorption of
the two nanofluids had achieved breakthroughs at any concentra-
tion. Specifically, Ti3C2Tx nanofluids achieved the maximum energy
absorption of 2985 J at the concentration of 20 ppm, which is about
4.5% higher than that of graphene nanofluids (2856 J). The gra-
phene nanofluid reached the maximum energy absorption of 2870 J
when the mass concentration is 40 ppm. The comparison results
once again prove that the MXene nanofluids could more effectively
capture solar radiation energy and convert it into thermal energy
due to its LSPR and unique optical properties. In addition, this also
shows the potential of its application in DASCs.
Photothermal conversion efficiency is a direct index to measure
the light energy utilization of DASC. Fig. 15(b) shows the PTC effi-
ciency of the two fluids as a function of concentration. The PTC
efficiency of Ti3C2Tx nanofluids is higher than that of graphene
nanofluids at each and every mass concentration. And the effi-
ciency of the two fluids shows obvious parabola with the increase
of concentration. The Ti3C2Tx nanofluids achieve the maximum
photothermal conversion efficiency of 63.35% at 20 ppm, which is
4.34% higher than that of graphene nanofluids. And the graphene
nanofluids reach the maximum efficiency of 60.92% at 40 ppm.
Subsequently, the conversion efficiency of the two kinds of nano-
fluids decreases with the further increase of concentration, which is
attributed to excessive heat loss. Through Fig. 15(b), it can be clearly
seen that the conversion efficiency of Ti3C2Tx nanofluids has
obvious advantages at low concentrations (<10 ppm). With the
further increase of the concentration, the photothermal conversion
efficiency of the two kinds of nanofluids tends to approach step by
step. There are four main explanations for this phenomenon: (1)
Ti3C2Tx nanofluids have the effect of plasmon [60] and stronger UV
absorption capacity, so it has a greater light absorption effect at the
same concentration. (2) As shown in Fig. 14, compared with gra-
phene nanofluids, Ti3C2Tx nanofluids have obvious surface ab-
sorption characteristics when the concentration is higher than
10 ppm, which means that the heat converted by Ti3C2Tx nanofluids
is mainly concentrated on the surface of the fluid, resulting in a
larger amount of heat loss. (3) As discussed in section 3.3, the
thermal conductivity of graphene nanofluids is higher, and this
advantage gradually expands with the increase of temperature.
High thermal conductivity helps nanofluids transfer heat from the
upper layer to the lower layer faster, thereby reducing the heat loss.
(4) The previous analysis of optical properties shows that the
transmittance of graphene nanofluids at high concentration is
higher than that of Ti3C2Tx nanofluids, which means that graphene
12
Energy 227 (2021) 120483
nanofluids can still ensure a deeper penetration distance for light at
high concentrations, allowing more particles participate in photo-
thermal conversion.
In order to further determine the optimal design conditions of
DASC, the local efficiency, that is, the photothermal conversion ef-
ficiency hy related to the fluid depth, is calculated by formula (8).

y
hcnf mi ðTj0  Tinitial
hy ¼ ðt (8)
GAdt
0
where h is the height of the sample, Tinitial is the initial temperature
of nanofluids, Tjy0 represents the temperature that is integrated to
the height y. The above analysis results in the optimal fluid con-
centration, and on this basis, the influence of fluid depth on effi-
ciency is further discussed. As shown in Fig. 16, the Ti3C2Tx
nanofluid with a concentration of 20 ppm achieves a high con-
version efficiency when the fluid depth is 3 cm, and further
increasing the fluid depth will not have a significant impact on the
efficiency improvement. However, the graphene nanofluids need a
deeper fluid depth because of its higher transmittance. When the
concentration is 40 ppm, about 3.5 cm of graphene nanofluid is
required.
4. Conclusion
In this study, the thermal conductivity and optical properties of
nanofluids based on two typical two-dimensional materials were
analyzed. And the photothermal conversion properties of the
nanofluids were evaluated by combining the nanofluids with DASC.
As far as we know, this is the first time to systematically study the
optical and photothermal conversion of water-based MXene
nanofluids. The main conclusions are as follows:
(1) In the comparative experiment of thermal conductivity, the
thermal conductivity of the two fluids shows an upward
trend with the increase of temperature and concentration. At
the same time, the graphene nanofluids show more promi-
nent thermal conductivity.
(2) The tests of optical properties showed that MXene is an
excellent optical material, which exhibits plasmon effect in
the near-infrared band. At the same time, the 60 ppm of
Ti3C2Tx nanofluid achieves a spectral transmittance of almost
H. Wang, X. Li, B. Luo et al.
Fig. 16. Photothermal conversion efficiency vs. collector height and mass concentration after irradiation time of 2500 s for (a) Mxene (b) graphene nanofluids (The solid line does
not represent data, but only serves as a trend indicator.).
0%, while the transmittance of graphene nanofluid under the
same conditions is still higher than 10%.
(3) The PTC efficiency of the two nanofluids is parabolic with the
increase of concentration. The Ti3C2Tx nanofluid reaches the
maximum photothermal conversion efficiency at 20 ppm,
which is 63.35%. The graphene nanofluid requires a con-
centration of 40 ppm to achieve the highest conversion ef-
ficiency, which is 60.92% lower than Ti3C2Tx nanofluid.
(4) Through the analysis of local photothermal conversion effi-
ciency, the conditions of DASC are further optimized. The
results show that the Ti3C2Tx nanofluid of 20 ppm only needs
the fluid depth of 3 cm to achieve the maximum conversion
efficiency, while the graphene nanofluid requires 3.5 cm.
Credit author statement
Xiaoke Li: Conceptualization, Methodology, Writing e original
draft preparation, Funding acquisition. Hao Wang: Investigation,
Data curation, Writing-Reviewing and Editing. Boqiu Luo: Re-
sources, Investigation, Visualization. Ke Wei: Software, Investiga-
tion. Guangyong Zeng: Conceptualization, Supervision
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
The authors would like to acknowledge the financial support of
Research Foundation of Chengdu University of Technology (10912-
2019KYQD-07545). The authors would like to acknowledge the
technical support of Ceshigo Research Service Agency (www.
ceshigo.com).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.energy.2021.120483.
13
Energy 227 (2021) 120483
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