Applied Thermal Engineering 147 (2019) 390–398

Contents lists available at ScienceDirect

Applied Thermal Engineering

journal homepage: www.elsevier.com/locate/apthermeng

Research Paper

Photo-thermal conversion properties of hybrid CuO-MWCNT/H2O T

nanofluids for direct solar thermal energy harvest
⁎
Jian Qu , Ruomei Zhang, Zhihao Wang, Qian Wang
School of Energy and Power Engineering, Jiangsu University, Zhenjiang, China

H I GH L IG H T S

• Optical and photo-thermal properties of hybrid CuO-MWCNT/H O nanofluids were experimentally tested.
2

• The extinction coefficients of hybrid nanofluids were largely equal to the sum of individual components.
• Then incoming solar radiation can be fully absorbed by hybrid nanofluids at 1 cm path length.
• AThemaximum terminal temperature rise of 14.1 °C was achieved for hybrid nanofluids with respect to DI water.
• interaction of CuO NPs and MWCNT fibers was responsible for the photo-thermal conversion performance enhancement.

A R T I C LE I N FO A B S T R A C T

Keywords:
Direct absorption solar collector
Nanofluid
Photo-thermal conversion performance
Optical absorption property
Solar weighted absorption fraction
Water-based hybrid nanofluids with CuO and multi-walled carbon nanotube (MWCNT) were prepared and well
dispersed. The optical absorption properties and photo-thermal conversion performance of hybrid CuO-
MWCNT/H2O nanofluids at different concentration mixing ratios (CMRs) were experimentally tested and
compared to evaluate the solar thermal energy harvest capability. The mixture of CuO-MWCNT nanofluids
significantly enhanced solar energy spectral absorption as compared with individual CuO or MWCNT nanofluids,
and the extinction coefficients of hybrid nanofluids were mostly equal to the sum of individual components. At
appropriate CuO/MWCNT CMRs, the solar weighted absorption fractions of hybrid nanofluids are almost 100%
at an optical penetration distance of 1 cm. Besides, the photo-thermal conversion performance of hybrid na-
nofluids was largely superior to individual nanofluids but highly dependent on the CMR, and an excessive
addition of individual component could lower the performance. At a CuO/MWCNT CMR of 0.15 wt%/0.005 wt
%, a maximum terminal temperature rise of 14.1 °C was achieved with respect to DI water after a light irra-
diation time duration of 45 min. The coexistence and interaction of CuO nanoparticles and MWCNT fibers in the
aqueous suspension at evaluated temperatures were took into account to explain the optical absorption behavior
and then the photo-thermal conversion properties. This study suggests that hybrid CuO-MWCNT/H2O nanofluids
at appropriate CMRs provide a potential alternative in direct solar thermal energy harvest.

1. Introduction
To data conventional energy sources based on fossil fuels are still
dominant with the highest share in global energy consumption around
the world, however the renewable energy has received growing interest
since the beginning of the new century due to the ever-increasing
amount of energy consumption as well as environmental concerns,
especially the CO2-emission induced global warming [1,2]. Solar en-
ergy is extensively used and considered as a promising solution among
diverse clean alternatives as it provides free, inexhaustible and en-
vironmentally friendly energy sources [3].
The solar energy comes directly from the sun radiation and can be
primarily converted into electricity and heat. Apart from directly gen-
erating electric power (usually using solar PV cells), more and more
attention is being paid to solar thermal energy harvesting as it exhibits
the tremendous practicability in different applications, such as thermal
storage, steam generation and electric power generation [1]. The con-
ventional surface-based tube/flat-plate solar thermal collector, which
absorbs the incident solar radiation and then transports to a heat
transfer fluid (HTF), suffered from relatively low efficiency due to much
heat loss. Owing to this shortage, direct absorption solar collectors
(DASCs) [4], absorbed the solar radiation directly and volumetrically

⁎
Corresponding author.
E-mail address: rjqu@mail.ujs.edu.cn (J. Qu).

https://doi.org/10.1016/j.applthermaleng.2018.10.094
Received 27 July 2018; Received in revised form 20 October 2018; Accepted 22 October 2018
Available online 22 October 2018
1359-4311/ © 2018 Elsevier Ltd. All rights reserved.
J. Qu et al.
by HTFs, were proposed to minimize the convection loss and further
improve the thermal efficiency [5,6] or even directly generate steam
[7,8].
Numerous studies shown that some commonly used HTFs such as
water, ethylene glycol and heat transfer oil seem to be inferior to their
nanofluids, which are produced by dispersing a small number of nan-
ometer-sized additives into base liquid, with respect to the selective
absorption of solar spectrum and photo-thermal conversion efficiency
[10,11]. Actually, the concentration of nano-materials required for
solar collectors is only on the scale of mg/L or tens of ppm, while it can
drastically improve optical absorption properties [9]. A low nano-
particle (NP) concentration ensures tiny cost addition from the base
fluid and, potentially, is responsible for the negligible change in visc-
osity as compared with that of pure liquid and high stability due to less
particle to particle interactions [9]. Consequently, dilute nanofluids are
commonly believed to be a promising alternative to conventional HTFs.
For solar thermal systems, diverse nanomaterials have been studied
involving metal [12–14], oxide [15–17] and carbon materials
[6,18,19]. In addition to mono NP based nanofluids, nanofluids con-
taining composite two or more NPs have also be attracted considerable
attention to tune the absorption spectra of working fluids [20]. As the
optical absorption spectra of nanofluid is largely determined by the NP
type, size and concentration, the combination of two or more composite
NPs provides the possibility to match the solar radiation spectra and
achieve a broadband, especially full-spectrum, volumetric solar thermal
absorption based on their complementary optical absorption properties.
Zhang et al. [21] experimentally compared the photo-thermal con-
version characteristics of several different nanofluids, and found that
the photo-thermal conversion efficiency increased in the order of Al2O3,
diamond, (Fe3O4 and Si) and Au NPs. Although the photo-thermal
conversion performance of hybrid nanofluid with composite Fe3O4-Au
NPs was remarkably better than that of the Au-based nanofluid, de-
graded performance of diamond-Au hybrid nanofluid was observed as
compared with that of Au and Fe3O4-Au nanofluids. Menbari et al. [22]
investigated the optical absorption and stability of Al2O3-CuO binary
nanofluid and evaluated the impact on the thermal efficiency of direct
absorption solar parabolic trough collectors (DASPTCs). Results re-
vealed that the increase of NP concentration and nanofluid flow rate
could upgrade the DASPTC efficiency. Taking advantage of the loca-
lized surface plasmon resonance (LSPR) effect, Au, Ag, and Au-Ag
blended hybrid nanofluids were prepared by Chen et al. [20] and their
photo-thermal conversion characteristics were evaluated experimen-
tally. They found that both of the temperature and photo-thermal
conversion efficiency were elevated with the increase of Au NP con-
centration. It is noteworthy that the photo-thermal conversion effi-
ciency of hybrid Au-Ag nanofluid was approximate to the arithmetic
sum of mono Au/Ag based nanofluids, which is largely attributed to the
separate absorption of different wavebands by Au and Ag NPs. Contrary
to above works, however, the most recent study by Zeiny et al. [23]
found that the Au-Cu hybrid nanofluids did not produce any additional
benefits as the photo-thermal conversion efficiency was not increased
by blending Au-Cu nanofluids with different absorbance peaks, and the
dilution of NP concentration accounts for the reduction of absorption
peak value even though the blending broadens the peak width. In ad-
dition, some other complex hybrid nanofluids composed of composite
core/shell NPs were prepared by Xuan’s group [24–26], and experi-
mental tests indicated that these nanofluids could achieve good photo-
thermal conversion performance due to the localized surface plasmon
resonance (LSPR) effect on the NP surface. Photonic nanofluids com-
posed of Janus type of magnetic-plasmonic Fe3O4/TiN nanoparticles
were prepared by Zeng and Xuan [26], and the LSPR of TiN in visible
wavelength and high absorption of Fe3O4 in near-infrared wavelength
enabled this nanofluid to largely achieve full-spectrum absorption of
incident solar energy.
In addition to alter the NP concentration in mono NP based nano-
fluids, the composite NP based nanofluids also exhibit the potential to
391
Applied Thermal Engineering 147 (2019) 390–398
enhance the photo-thermal conversion and collector efficiency in
DASCs though there existed discrepancies and still in progress. The
photo-thermal conversion experiments associated with binary nano-
fluids composed of metal-oxide/metal, double metal-oxide and double
metal NPs have already been conducted in recent years, however little
work was reported on the hybrid metal-oxide/carbo-material or metal/
carbo-material nanofluids. Despite the advantage of absorption en-
hancement by LSPR excitation that some noble metal NPs such as Au
and Ag and core/shell composite NPs are labeled, metal-oxides featured
by high absorption properties are more economically feasible and be-
come attractive for large-scale applications.
Our recent works on aqueous suspension of CuO with NPs produced
by the precursor transformation method revealed that it had high ab-
sorption properties and was a suitable candidate for DASCs [16]. As for
the carbon-material, the MWCNT-based nanofluid was highly suggested
as it is capable of absorbing over the majority of solar spectrum at ultra-
low concentrations [27]. Therefore, the hybrid CuO-MWCNT nanofluid
was selected in this study to compare the photo-thermal conversion
performance. The transmittance, extinction coefficient, and solar
weighted absorption fraction of individual nanofluids and hybrid na-
nofluids at different wavelengths were measured and compared, and
their photo-thermal conversion performance were experimentally
tested as well. The variations of optical absorption and photo-thermal
conversion performance of hybrid nanofluids with different nanoma-
terial concentration mixing ratios (CMRs) were analyzed and discussed.
This study provides an insight into the understanding of photo-thermal
conversion characteristics of metal-oxide/CNT composite nanofluids
and a possible solution with respect to nanofluid selection for direct
solar thermal energy harvest.
2. Experimental section
2.1. Synthesis and characterization of nanofluids
To prepare the hybrid nanofluids, CuO/H2O nanofluids (samples in
Fig. 1(a)) were firstly synthesized using a novel precursor transforma-
tion method as described in our recent work [16]. Then, the aqueous
suspension of MWCNTs purchased from Organic Chemistry Ltd. of
Chinese Academy of Sciences (Chengdu, China) was added into CuO/
H2O nanofluids under magnetic stirring to further improve the stability
and dispersion uniformity. Some characteristic parameters of the
MWCNTs were listed in Table 1. Finally, the hybrid CuO-MWCNT/H2O
nanofluids were obtained at different admixture concentrations as dis-
played in Fig. 1(b). After a month stay, no obvious precipitations were
observed at the bottom of cuvettes as shown in Fig. 1(c), implying that
hybrid nanofluids exhibit high dispersion stability against aggregation.
Fig. 2(a) depicts the transmission electronic microscope (TEM) image of
size and morphology of dispersed CuO NPs. It can be seen that spherical
CuO NPs are well dispersed with relatively uniform particle size dis-
tribution. As for the hybrid CuO-MWCNT/H2O nanofluid, CuO NPs
were largely distributed among MWCNT fibers uniformly and some NPs
were adsorbed onto the fiber surfaces as displayed in Fig. 2(b).
2.2. Optical absorption properties
To compare the optical absorption characteristics of CuO/H2O and
hybrid CuO-MWCNT/H2O nanofluids, the transmission spectra were
measured in a wavelength range from 200 to 2000 nm on a UV–Vis–NIR
spectrophotometer (Lambda 950) using same cuvettes (10 mm in op-
tical path length). Each measurement was repeated for three times to
eliminate the error of multiple reflections and scattering at the inter-
faces between air, quartz glass and liquid. According to the Lambert-
Beer law, the extinction coefficient of the tested sample can be calcu-
lated by
J. Qu et al. Applied Thermal Engineering 147 (2019) 390–398

−ln[T (λ )]
K eλ =
y (1)

where T (λ) is the spectral transmittance, and y is the optical-path

length (i.e., 10 mm).

2.3. Photo-thermal conversion experiment

Fig. 3 shows the experimental setup to evaluate the photo-thermal

conversion performance of hybrid CuO-MWCNT/H2O nanofluids. Be-
fore the test, same amounts of nanofluids at different CMRs and DI
water were respectively added into several high borosilicate double-
layer vacuum glass tubes (92% light transmittance, 30 mm inside dia-
meter, 45 mm outside diameter, and 200 mm length) to ensure the same
light absorption area. Owing to the liquid thermal expansion caused by
temperature rise, a little space was reserved between the liquid level
and rubber plug to prevent liquid leakage. All tubes were placed in an
insulation box made of styrofoam block (thermal conductivity of
0.038 W/(m·K)) to minimize the heat loss. The styrofoam block was
shielded from incident radiation with aluminized paper so as to reduce
the absorption of sunlight and avoid the heating effect toward the
surrounded glass tubes. The insulation box was tilted and kept at a
horizontal angle of about 30°. A solar simulator (TRM-PD, Jinzhou
Sunshine Technology), which matches with the AM1.5 spectrum well
and meets ASTM Class A, was employed as a radiative source.
During the experiment, the radiation from solar simulator was
beamed down to an array of receiver tubes, and the radiative flux in-
cident onto the tube cover was precisely recorded by a solar radiation
meter (TBQ-2). The solar intensity was maintained at 965 ± 10 W/m2
at an ambient temperature of 25 ± 1 °C. The average temperature of
nanofluid in each tube was determined by two T-type thermocouples
(OMEGA, 0.1 mm diameter) placed at its centerline. All temperature
measurements were implemented by a data logger (34970A, Agilent)
for real-time acquisition.

3. Results and discussion

This section begins with the spectral transmittance, extinction

coefficient, and solar weighted absorption fraction of nanofluids to in-
dicate the photo-absorption properties. Then, the transient temperature
variations of hybrid nanofluids at different CMRs are given and the
optimal concentration ratio with respect to highest temperature rise at
the same irradiation time duration is determined. Besides, the under-
lying mechanism that affects the photo-thermal conversion perfor-
mance using hybrid nanofluids is preliminarily analyzed and explained.

3.1. Optical properties of hybrid nanofluids

3.1.1. Spectral transmittance

Fig. 4 compares the spectral transmittances of CuO/H2O and hybrid
CuO-MWCNT/H2O nanofluids at different concentrations. As for DI
water, it is regarded as a reference for these two nanofluids with a nano-
additive mass fraction of zero. In Fig. 4(a), it can be seen that the
Fig. 1. CuO/H2O nanofluids (a), hybrid CuO-MWCNT/H2O nanofluids as-pre- transmittance of DI water is close to 100% within the ultraviolet to
pared (b) and after 1-month stay (c) at different admixture concentrations (CuO visible region and thus hardly absorbs light, while it can absorb a
mass fractions: 1. 0.25%, 2. 0.15%, 3. 0.05%, 4. 0.025%, 5. 0.01%; MWCNT majority of solar radiation above 1350 nm for the sake of direct solar
mass fraction: 0.0015%).
collection regardless of the addition of CuO NPs. Compared with DI
water, the transmittances of CuO/H2O nanofluids decreased with in-
Table 1 creasing the NP concentration within a wavelength range of
Characteristic parameters of MWCNTs. 200–1350 nm, which is attributed to the enhancement of optical ab-
Purity Inner diameter Outer diameter Length (μm) Preparation sorption and scattering. It is noteworthy that the high transmittance of
(nm) (nm) method 0.01–0.05 wt% nanofluids around 470 nm in the visible region and an
abrupt drop at the higher NP concentration of 0.15 wt% can be evi-
> 95% 5–15 > 50 10–20 CVD
denced by the color difference in Fig. 1(a) as discussed in our previous
work [16].
Fig. 4(b) presents a typical transmittance variation after the

392
J. Qu et al.
Fig. 2. TEM images of CuO/H2O nanofluid (a) and hybrid CuO-MWCNT/H2O nanofluid (b).
Fig. 3. Experimental setup of nanofluid photo-thermal conversion performance (1. solar simulator; 2. double-layer vacuum glass tubes containing nanofluids; 3. solar
radiation meter; 4. thermocouples; 5. solar radiation recorder; 6. data logger; 7. computer).
addition of MWCNTs with the CuO concentrations remained unchanged
with respect to Fig. 4(a). Compared with CuO/H2O nanofluids, a sig-
nificant reduction of transmittance was observed after the addition of
MWCNTs owing to its desirable photo-absorption capability in ac-
cordance with the mono MWCNT/H2O nanofluid (0.0015 wt%).
Moreover, compared to the MWCNT/H2O nanofluid, the transmittance
of hybrid nanofluid was also reduced remarkably. Particularly, the
transmittance of hybrid nanofluid with the CuO/MWCNT CMR of
0.25 wt%/0.0015 wt% dropped closely to zero in the wavelength range
of 200–2000 nm, indicating the fully-spectrum absorption. But for the
0.25 wt% CuO/H2O nanofluid (see Fig. 4(a)), its transmittance was only
about 55% around the 1080 nm wavelength, implying that its optical
absorption performance is inferior to the hybrid nanofluid. For the
CuO/H2O nanofluid with a lower mass fraction of 0.15%, the reduction
in transmittance after the addition of MWCNTs is also remarkable. In-
terestingly, although the transmittance of CuO/H2O nanofluids largely
decreased with the increase of NP concentration as shown in Fig. 4(a),
the addition of MWCNTs partially deviated from this trend (see
Fig. 4(b)) and some sort of opposite results were observed around the
crest points of 515, 915, 1080, and 1260 nm with the CuO NP con-
centration varied ranging from 0.01 to 0.05 wt%, namely the trans-
mittance of hybrid nanofluids increased with NP concentration. By
comparing these transmittance curves of 0.01 wt%, 0.025 wt%, and
0.05 wt% nanofluids in Fig. 4(a), it can be found that their fluctuation
amplitudes around above crest points increase with the increase of
nanofluid concentration, and the oscillating inertia with respect to each
transmittance curve may be largely remained even after adding the
393
Applied Thermal Engineering 147 (2019) 390–398
MWCNT material in Fig. 4(b), namely the relative magnitude of fluc-
tuation amplitude can be inherited. This is the possible explanation for
above deviation and the trough points of transmittance curves at about
745 and 970 nm (fluctuation amplitudes decrease with the increase of
nanofluid concentration) in Fig. 4(a) and the resultant oscillating in-
ertia at the corresponding wavelengths in Fig. 4(b) can partially verify
this assumption.
3.1.2. Extinction coefficient
Compared with the transmittance, the extinction coefficient is an-
other crucial parameter to evaluate the optical absorption and scat-
tering properties. If the NPs are uniformly distributed and have small
size, scattering fraction is usually negligibly small and can be neglected
[23,28]. Therefore, the extinction coefficient in this study can be ap-
proximately used to evaluate the optical absorption capability of na-
nofluids. Fig. 5 compares the spectral extinction coefficients of CuO/
H2O nanofluids, MWCNT/H2O nanofluids and the mixture of them at
different concentrations. Since the light was fully absorbed after the
addition of MWCNT materials when the wavelength is greater than
about 1350 nm (see Fig. 4(b)), a smaller wavelength range of 200–1350
is highlighted herein.
As for 0.0015 wt% MWCNT, the extinction coefficients of hybrid
nanofluids were approximately equal to the sum of individual CuO/H2O
and MWCNT/H2O nanofluids, regardless of the concentration variation
of CuO NPs (i.e., 0.01 wt% in Fig. 5(a) and 0.05 wt% in Fig. 5(b)),
especially at the visible light region. With a further increase of MWCNT
concentration, the extinction coefficients of MWCNT/H2O nanofluids
J. Qu et al. Applied Thermal Engineering 147 (2019) 390–398

Fig. 4. Transmittances of CuO/H2O nanofluids (a) and hybrid CuO-MWCNT/

H2O nanofluids (b) at different concentrations.

were increased, signifying that MWCNT/H2O nanofluid at a con-

centration of 0.005 wt% were almost impermeable to sunlight and ac-
count for full absorption, and hence the extinction coefficients of hybrid
nanofluids are close to 10 cm−1 (see Fig. 5(c)). Whether the con-
centration of an individual nanomaterial component (CuO or MWCNT)
is low or high, the photo-absorption properties of hybrid nanofluids are
actually nearly equal to the sum of individual nanomaterials in the base
fluid, which is consistent with the results by Menbari et al. [29] using
Al2O3-CuO binary NPs dispersed in ethylene glycol.

3.1.3. Solar weighted absorption fraction

The evidenced spectrally-resolved optical properties provide insight
into the underlying sunlight extinction characteristics of nanofluids as
well as their energy storage capability [30], which is fundamentally
important for the absorption fluid selection and collector structure
optimization. To quantitatively evaluate the solar absorption capability
of nanofluids, the solar weighted absorption fraction (absorbed energy
fraction) F of incident sunlight that after an optical path length x within
the sample, namely unable to be transmitted and has been stored in the
nanofluid (also including the light scattering contribution in addition to
Fig. 5. Extinction coefficient comparison of different nanofluids (‘a + b’ de-
the direct absorption), is given by the expression:
notes the sum of the extinction coefficients of CuO/H2O and MWCNT/H2O).
λmax
∫λmin IAM1.5 (λ )e−K (λ) x dλ
F=1− λ discrete values, an integration of Eq. (2) is required to obtain the
max
∫λmin IAM1.5 (λ )dλ (2) summations.
where IAM1.5 is the AM1.5 solar spectrum in light of ASTMG173 [31] at According to Eq. (2), it can be found that the solar weighted ab-
the wavelength range of 280–2000 nm. The thickness of nanofluid layer sorption fractions of nanofluids are largely dependent on the product of
x can be also considered as the height of a DASC. As the spectral extinction coefficient and optical path length (or thickness of nanofluid
properties and the spectral irradiance are normally known only as layer), and the optical absorption capability increases with both of

394
J. Qu et al. Applied Thermal Engineering 147 (2019) 390–398

collector height should be consistent with the optical path length, it can
be concluded that a small collector height is theoretically suggested to
improve DASC efficiency. If the collector height is too low, however,
the solar energy can not be thoroughly absorbed by the nanofluid,
degrading the receiver efficiency significantly. Therefore, the collector
height should be optimized in terms of the nanoparticle weight per-
centage to achieve the maximum efficiency.
Compared to CuO/H2O nanofluids, the addition of MWCNT and
resultant hybrid CuO-MWCNT/H2O nanofluids can greatly enlarge F
and the fully energy absorption is achieved after adding 0.0015 wt%
MWCNT as displayed in Fig. 6(b). Clearly, the use of MWCNT
(0.0015 wt%) does not change the variation trend of F with respect to
weight percentage dependent of CuO on the absorbed energy fraction
and it increases with the CuO concentration similar to Fig. 6(a). For the
hybrid nanofluids, the absorbed energy fraction can reach 99.2% or
more when the CuO concentration is equal to or greater than 0.15 wt%
at 1 cm path length. Consequently, the further increase of MWCNT
concentration can completely absorb the incoming energy radiation
within a thinner top layer of the hybrid nanofluid rather than volu-
metrically by the fluid medium and subsequently the system ap-
proaches the surface-based collector. Besides, excessive MWCNT may
cause aggregation and lower suspension stability, lowering the photo-
thermal conversion properties of DASC. Therefore, the appropriate
nanomaterial concentration and CMR are required to improve the DASC
efficiency.

3.2. Photo-thermal conversion performance of hybrid nanofluids

Fig. 7 shows the temperature variations of CuO/H2O nanofluids at

different concentrations ranging from 0 (DI water) to 0.25 wt% as ex-
posed to light during the experiment. It can be seen that the photo-
thermal conversion performance of pure water is apparently enhanced
after the addition of CuO NPs, and the temperature rise of CuO/H2O
nanofluids increased with the increase of NP concentration, which is in
accordance with the reduction of transmittance as increasing CuO
concentration (see Fig. 4(a)). Owing to the introduction of CuO NPs, the
optical scattering and absorption can be greatly enhanced, and then
improves the overall photo-thermal conversion capacity of working
Fig. 6. Solar weighted absorption fraction versus the penetration distance for
fluid. At the maximum concentration of 0.25 wt%, the temperature of
the CuO/H2O nanofluids (a) and CuO-MWCNT/H2O nanofluids (b) at different
CuO/H2O nanofluid was increased by 9.2 °C with respect to DI water
mass fractions.
after the light irradiation duration of 45 min.
Fig. 8 shows the temperature variations of hybrid CuO-MWCNT/
them, which is responsible for the performance improvement of DASCs H2O nanofluids at different CMRs. Compared with CuO/H2O nano-
[32]. As mentioned earlier, the extinction coefficient is determined by fluids, the photo-thermal conversion performance was further improved
the nano-material type, concentration and CMR in the nanofluid and after the addition of MWCNTs with a low mass fraction of 0.015% (see
utilized for the evaluation of optical absorption. If the extinction coef-
ficient is given, the optical path length associated with the collector
height becomes the key parameter to affect the DASC performance.
The solar weighted absorption fractions of CuO/H2O nanofluids
with different concentrations at varying penetration distance (x) are
displayed in Fig. 6(a). It can be seen that the absorbed energy fraction
increases with the CuO concentration at each penetration distance
(> 0 cm), while it is still lower than 90% even after a 10 cm-long
propagation path for CuO mass fractions ranging from 0.01 wt% to
0.1 wt%. However, it is as low as 30% for pure water after a same
propagation path, definitely demonstrating the beneficial effect of na-
noparticle addition on efficient solar energy storage. As for the rela-
tively high concentration of 0.15 wt%, it can also only achieve partial
energy absorption at the penetration distance of 10 cm (about 97%);
and a fully absorption is achieved at the highest concentration of
0.25 wt% with the absorbed energy fraction being up to about 99% at
3.5 cm path length. Moreover, we can find that the value of F is greater
than 50% at 1.25 cm path length for relatively high CuO concentrations
ranging from 0.1 wt%–0.25 wt% in Fig. 6(a), indicating that most of the
incoming solar radiation is absorbed in such a thin fluid layer. Since the Fig. 7. Temperature variations of CuO/H2O nanofluids at different concentra-
tions.

395
J. Qu et al.
Fig. 8. Temperature variations of hybrid CuO-MWCNT/H2O nanofluids at dif-
ferent CMRs.
Fig. 8(a)), and the temperature rise increased with the CuO con-
centration similar to that in Fig. 7. After being irradiated for 45 min, the
terminal temperatures were increased by 3.7, 3.8, 4.2, 3.7 and 4.0 °C,
respectively, in comparison with that of 0.01 wt%, 0.025 wt%, 0.05 wt
%, 0.15 wt% and 0.25 wt% CuO/H2O nanofluids without MWCNT
396
Applied Thermal Engineering 147 (2019) 390–398
materials. Encouragingly, the photo-thermal conversion performance of
hybrid CuO-MWCNT/H2O nanofluids was also largely better than
commonly suggested MWCNT/H2O nanofluids, depending on the
MWCNT concentration. At low and moderate concentrations (0.0015 wt
% and 0.005 wt%), the terminal temperatures of hybrid nanofluids
were greater than that of single component MWCNT/H2O nanofluids
(see Fig. 8(a and b)), while a reverse result was observed as the MWCNT
concentration was increased up to 0.01 wt% (see Fig. 8(c)). Table 2 lists
the corresponding terminal temperatures of hybrid nanofluids after a
light irradiation time duration of 45 min. As for hybrid nanofluids, it
can be seen that the maximum terminal temperature rises were 4.4 and
3.9 °C with CuO-MWCNT CMRs of 0.25 wt%/0.0015 wt% and 0.15 wt
%/0.005 wt%, respectively, as compared to MWCNT/H2O nanofluids at
corresponding concentrations of 0.0015 wt% and 0.005 wt%. However,
a further increase of MWCNT concentration (0.01 wt%) caused per-
formance deterioration of hybrid nanofluids. For instance, the terminal
temperature rise of hybrid CuO-MWCNT nanofluids at a CMR of 0.25 wt
%/0.01 wt% was decreased by 2.4 °C than that of single component
MWCNT/H2O nanofluid (0.01 wt%). Therefore, the excessive addition
of MWCNT into CuO/H2O nanofluids greatly altered the monotonic
influence of CuO concentration on the temperature rise as shown in
Fig. 7.
For hybrid nanofluids involving MWCNT material of 0.005 wt%
concentration as displayed in Fig. 8(b), the photo-thermal conversion
capability increased initially and then decreased with increasing CuO
concentration. An optimum CuO concentration of about 0.15 wt% was
observed associated with the highest terminal temperature of 80.1 °C
after a light irradiation time duration of 45 min (see Table 2), which is
3.9 °C higher than that of single component MWCNT/H2O nanofluid
(0.005 wt%) and 14.1 °C higher than that of DI water, while a further
increase of CuO NPs reduced the temperature rise, despite that it is
superior to that of individual MWCNT/H2O nanofluids. At a high
MWCNT concentration of 0.01 wt% as shown in Fig. 8(c), the addition
of CuO NPs totally degraded the mixture performance even at a low
CuO mass fraction of 0.01% (see Table 2), but still much better than
that of DI water. According to our recent work on the photo-thermal
conversion properties of single component MWCNT/H2O nanofluids
[18], a critical saturation concentration of 0.01 wt% with respect to the
best light energy absorption at elevated temperatures was identified.
Therefore, it can be concluded that the addition of metal-oxide NPs into
MWCNT-H2O nanofluids at or over the saturation concentration is
detrimental to its overall energy absorption, while it remains to be in-
vestigated for other nanocomposites involving MWCNTs and metal-
oxide/metal NPs.
In addition to the nature of individual CuO NPs or MWCNT fibers,
the interaction of them also partially affects the photo-thermal con-
version performance and should be considered. Actually, the coex-
istence of CuO NPs and MWCNT fibers in the aqueous suspension di-
rectly determines the mutual position distribution of particle-fiber
system and the resultant individual aggregation. Obviously, the ag-
gregation, stability and deposition of particle-fiber system are CMR
dependent and excessive concentration of an individual component
could lower performance in photo-thermal conversion as shown in
Fig. 8. The possible mechanism is proposed by taking into account the
special role played by CuO NPs as schematically illustrated in Fig. 9. As
for single component MWCNT-H2O nanofluids, a relatively lower con-
centration with appropriate CNT fiber agglomeration at elevated tem-
peratures is beneficial to the performance improvement. The addition
of CuO NPs can further enhance photo-thermal conversion performance
owing to the reciprocal optical absorption enhancement with uniformly
distributed CuO NPs among CNT fibers. That is to say, the increase of
CuO NP concentration is favorable to the photo-thermal conversion
performance of the hybrid nanofluid at low MWCNT concentration (see
Fig. 8(a)). Although CuO-MWCNT nanocomposites allow some CuO
NPs to be adsorbed onto the surface of MWCNT fibers and may degrade
the optical absorbance of fibers, the photo-thermal conversion behavior
J. Qu et al. Applied Thermal Engineering 147 (2019) 390–398

Table 2
Summary of terminal temperatures of hybrid CuO-MWCNT/H2O nanofluids at different admixture concentrations after a light irradiation time duration of 45 min.
MWCNT Concentration/(0 wt%) T/°C Concentration/(0.0015 wt%) T/°C Concentration/(0.005 wt%) T/°C Concentration/(0.01 wt%) T/°C

CuO 0 66.0 0 74.8 0 76.2 0 79.9

0.01 72.4 0.01 76.1 0.01 77.8 0.01 79.6
0.025 73.1 0.025 76.9 0.025 78.6 0.025 79.4
0.05 73.7 0.05 77.9 0.05 79.5 0.05 79.2
0.15 74.6 0.15 78.3 0.15 80.1 0.15 78.8
0.25 75.2 0.25 79.2 0.25 78.1 0.25 77.5

Fig. 9. Schematic diagram of CuO-MWCNT composites at different MWCNT concentrations.

of hybrid aqueous suspension seems to be negligibly affected by the
coverage behavior.
With the increase of MWCNT concentration, however, the tem-
perature rise can cause aggregation intensification of CNT-fibers and
aggravate suspension instability. If CNT-fiber agglomerates are grew to
a size towards the occurrence of obvious sedimentation, the CNT-fiber
concentration would decrease accordingly and thus lower the photo-
thermal conversion performance. At the moderate MWCNT concentra-
tion of 0.005 wt%, there existed an optimal CuO concentration of
0.15 wt% with respect to the best photo-thermal conversion perfor-
mance and more CuO NPs could cause terminal temperature drop (see
Table 2). The early appearance of saturation concentration in com-
parison with mono MWCNT/H2O nanofluids implies that CuO NPs can
produce additional MWCNT aggregation or aggravate it at evaluated
temperature, which lowers the suspension stability. When the MWCNT
concentration is increased to 0.01 wt%, the photo-thermal conversion
performance of hybrid nanofluid was aggravated further by the fiber
agglomeration, and hence the addition of CuO NPs could hardly im-
prove the optical absorption ability but further deteriorated it. Besides,
at a high MWCNT concentration, the dispersed MWCNT fibers would
reflect more light, and the reduction in incident light resulted in less
heat generation and decreased the maximum temperature eventually.
4. Conclusions
In this paper, hybrid CuO-MWCNT/H2O nanofluids were prepared
and utilized for evaluating the optical-absorption property and photo-
thermal conversion performance under different CMRs. It becomes a
promising solution for direct solar thermal energy harvest, and the
main conclusions are drawn as follows:
MWCNT (0.0015 wt%) in the CuO/H2O nanofluid can significantly
increase the optical absorption capability of hybrid nanofluids, and
the incoming solar radiation is almost fully absorbed when the CuO
concentration is equal to or greater than 0.15 wt% at 1 cm path
length. To achieve the maximum efficiency of a DASC, the solar
collector height and nanomaterial concentration and CMR should
be overall considered.
(3) For the hybrid CuO-MWCNT/H2O nanofluids, its photo-thermal
conversion performance was sensitive to CMRs and excessive ad-
dition of an individual component lowered performance. At a
moderate MWCNT concentration of 0.005 wt%, the terminal tem-
peratures increased initially and then decreased with increasing the
CuO concentration, and the terminal temperature rise of hybrid
nanofluid was 14.1 °C higher than that of DI water at an optimum
CuO concentration of 0.15 wt%.
(4) The reciprocal optical absorption enhancement with uniformly
distributed CuO NPs among CNT fibers enables higher photo-
thermal conversion performance of hybrid nanofluids, even though
CNT fibers may be partially coated with CuO NPs. However, CuO
NPs could produce additional MWCNT aggregation or aggravate it
at evaluated temperature and thus lower suspension stability at
high MWCNT concentrations and then the overall photo-thermal
conversion performance.
Acknowledgements
This work was financially supported by the National Nature Science
Foundation of China (No. 51576091).
References

(1) The transmittance of CuO/H2O nanofluids was significantly de-
creased after the addition of MWCNTs, and the spectral absorption
characteristics of hybrid CuO-MWCNT/H2O nanofluids were su-
perior to that of MWCNT/H2O nanofluids as well. Besides, the op-
tical absorption properties of hybrid nanofluids were almost equal
to the sum of individual CuO/H2O and MWCNT/H2O nanofluids at
a wavelength range of 200–1350 nm.
(2) Most of the incoming solar radiation (> 50%) could be absorbed in
a thin fluid layer of 1.25 cm for CuO/H2O nanofluids as con-
centrations varied from 0.1 wt%–0.25 wt%. The tiny addition of
[1] Y. Tian, C.Y. Zhao, A review of solar collectors and thermal energy storage in solar
thermal applications, Appl. Energy 104 (2013) 538–553.
[2] S.K. Verma, A.K. Tiwari, Progress of nanofluid application in solar collectors: a
review, Energy Convers. Manage. 100 (2015) 324–346.
[3] A.N. Al-Shamani, M.H. Yazdi, M.A. Alghoul, A.M. Abed, M.H. Ruslan, S. Mat,
K. Sopian, Nanofluids for improved efficiency in cooling solar collectors-a review,
Renew. Sustain. Energy Rev. 38 (2014) 348–367.
[4] T.P. Otanicar, P.E. Phelan, R.S. Prasher, G. Rosengarten, R.A. Taylor, Nanofluid-
based direct absorption solar collector, J. Renew. Sustain. Energy 2 (2010) 033102.
[5] H. Tyagi, P. Phelan, R. Prasher, Predicted efficiency of a low-temperature nano-
fluid-based direct absorption solar collector, J. Sol. Energy Eng. 131 (2009) 041004.
[6] L. Chen, C. Xu, J. Liu, X. Fang, Z. Zhang, Optical absorption property and photo-
thermal conversion performance of graphene oxide/water nanofluids with excellent

397
J. Qu et al.
dispersion stability, Sol. Energy 148 (2017) 17–24.
[7] R.A. Taylor, P.E. Phelan, R.J. Adrian, A. Gunawan, T.P. Otanicar, Characterization
of light-induced, volumetric steam generation in nanofluids, Int. J. Therm. Sci. 56
(2012) 1–11.
[8] H. Jin, G. Lin, L. Bai, A. Zeiny, D. Wen, Steam generation in a nanoparticle-based
solar receiver, Nano Energy 28 (2016) 397–406.
[9] R. Taylor, S. Coulombe, T. Otanicar, P. Phelan, Small particles, big impacts: a re-
view of the diverse applications of nanofluids, J. Appl. Phys. 113 (2013) 011301.
[10] A. Lenert, E.N. Wang, Optimization of nanofluid volumetric receivers for solar
thermal energy conversion, Sol. Energy 86 (2012) 253–265.
[11] Q. Li, C. Zheng, S. Mesgari, Y.L. Hewkuruppu, N. Hjerrild, F. Crisostomo,
G. Rosengarten, J.A. Scott, R.A. Taylor, Experimental and numerical investigation
of volumetric versus surface solar absorbers for a concentrated solar thermal col-
lector, Sol. Energy 136 (2016) 349–364.
[12] H. Tyagi, V. Khullar, P.E. Phelan, T.P. Otanicar, H. Singh, R.A. Taylor, Solar energy
harvesting using nanofluids-based concentrating solar collector, J. Nanotechnol.
Eng. Med. 3 (2012) 259–267.
[13] H. Zhang, H.J. Chen, X. Du, D. Wen, Photothermal conversion characteristics of
gold nanoparticle dispersions, Sol. Energy 100 (2014) 141–147.
[14] M. Chen, Y. He, J. Zhu, D. Wen, Investigating the collector efficiency of silver na-
nofluids based direct absorption solar collectors, Appl. Energy 181 (2016) 65–74.
[15] M. Milanese, G. Colangelo, A. Cretì, M. Lomascolo, F. Iacobazzi, A.D. Risi, Optical
absorption measurements of oxide nanoparticles for application as nanofluid in
direct absorption solar power systems – Part I: water-based nanofluids behavior,
Sol. Energy Mater. Sol. Cells 147 (2016) 315–320.
[16] R. Zhang, J. Qu, M. Tian, X. Han, Q. Wang, Efficiency improvement of a solar direct
volumetric receiver utilizing aqueous suspensions of CuO, Int. J. Energy Res. 42
(2018) 2456–2464.
[17] A. Menbari, A.A. Alemrajabi, A. Rezaei, Heat transfer analysis and the effect of
CuO/Water nanofluid on direct absorption concentrating solar collector, Appl.
Therm. Eng. 104 (2016) 176–183.
[18] S. Delfani, M. Karami, M.A. Akhavan-Behabadi, Performance characteristics of a
residential-type direct absorption solar collector using MWCNT nanofluid, Renew.
Energy 87 (2016) 754–764.
[19] J. Qu, M. Tian, X. Han, R. Zhang, Q. Wang, Photo-thermal conversion character-
istics of MWCNT-H2O nanofluids for direct solar thermal energy absorption appli-
cations, Appl. Therm. Eng. 124 (2017) 486–493.
[20] M. Chen, Y. He, J. Huang, J. Zhu, Synthesis and solar photo-thermal conversion of
398
Applied Thermal Engineering 147 (2019) 390–398
Au, Ag, and Au-Ag blended plasmonic nanoparticles, Energy Convers. Manage. 127
(2016) 293–300.
[21] H. Zhang, H.J. Chen, X. Du, G. Lin, D. Wen, Dependence of photothermal conver-
sion characteristics on different nanoparticle dispersions, J. Nanosci. Nanotechnol.
15 (2015) 3055–3060.
[22] A. Menbari, A.A. Alemrajabi, A. Rezaei, Experimental investigation of thermal
performance for direct absorption solar parabolic trough collector (DASPTC) based
on binary nanofluids, Exp. Therm. Fluid Sci. 80 (2017) 218–227.
[23] A. Zeiny, H. Jin, L. Bai, G. Lin, D. Wen, A comparative study of direct absorption
nanofluids for solar thermal applications, Sol. Energy 161 (2018) 74–82.
[24] Y. Xuan, H. Duan, Q. Li, Enhancement of solar energy absorption using a plasmonic
nanofluid based on TiO2/Ag composite nanoparticles, RSC Adv. 4 (2014)
16206–16213.
[25] J. Zeng, Y. Xuan, H. Duan, Tin-silica-silver composite nanoparticles for medium-to-
high temperature volumetric absorption solar collectors, Sol. Energy Mater. Sol.
Cells 157 (2016) 930–936.
[26] J. Zeng, Y. Xuan, Tunable full-spectrum photo-thermal conversion features of
magnetic plasmonic Fe3O4/TiN nanofluid, Nano Energy 51 (2018) 754–763.
[27] N. Hordy, D. Rabilloud, J.L. Meunier, S. Coulombe, High temperature and long-
term stability of carbon nanotube nanofluids for direct absorption solar thermal
collectors, Sol. Energy 105 (2014) 82–90.
[28] R.A. Taylor, P.E. Phelan, T.P. Otanicar, R. Adrian, R. Prasher, Nanofluid optical
property characterization: towards efficient direct absorption solar collectors,
Nanoscale Res. Lett. 6 (2011) 225.
[29] A. Menbari, A.A. Alemrajabi, Y. Ghayeb, Experimental investigation of stability and
extinction coefficient of Al2O3-CuO binary nanoparticles dispersed in ethylene
glycol–water mixture for low-temperature direct absorption solar collectors, Energy
Convers. Manage. 108 (2016) 501–510.
[30] E. Sani, S. Barison, Pagura, Mercatelli, Sansoni, Fontani, Jafrancesco, F. Francin,
Carbon nanohorns-based nanofluids as direct sunlight absorbers, Opt. Express 18
(2010) 5179–5187.
[31] ASTM G173-03, Standard Tables for Reference Solar Spectral Irradiances: Direct
Normal and Hemispherical on 37° Tilted Surface, ASTM, West Conshohocken, USA,
2012.
[32] L. Zhang, J. Liu, G. He, Z. Ye, X. Fang, Z. Zhang, Radiative properties of ionic liquid-
based nanofluids for medium-to-high-temperature direct absorption solar collec-
tors, Sol. Energy Mater. Sol. Cells 130 (2014) 521–528.