Renewable Energy 141 (2019) 937e949

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Solar photothermal conversion characteristics of hybrid nanofluids:

An experimental and numerical study
Xin Jin a, Guiping Lin a, Aimen Zeiny b, c, Haichuan Jin a, *, Lizhan Bai a, Dongsheng Wen a, b
a
Laboratory of Fundamental Science on Ergonomics and Environmental Control, School of Aeronautic Science and Engineering, Beihang University, Beijing,
100191, PR China
b
School of Chemical and Process Engineering, University of Leeds, Leeds, LS2 9JT, UK
c
Department of Mechanical Engineering, Faculty of Engineering, University of Kufa, Iraq

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

Article history: In this work, the Fe3O4, Cu and Au with different concentrations and the hybrid nanofluids were prepared
Received 24 January 2019 and characterized to enhance the solar photothermal conversion performance based on the direct ab-
Received in revised form sorption concept. An extensive experimental study was carried out with different sample nanofluids
30 March 2019
under a solar simulator. The experiment was first conducted with Au nanofluid in three cases to
Accepted 4 April 2019
Available online 5 April 2019
investigate the effect of different test conditions, and the test condition where the simulated sunlight
was absorbed by the sample nanofluid only once with minimum heat loss to the surroundings was
determined for later research. Based on the experimental results, below conclusions have been reached:
Keywords:
Solar energy
1) the solar energy absorption performance of nanofluids with plasmonic nanomaterials, i.e., Au or Cu, is
Nanofluids much better than that of nanofluids with non-plasmonic nanomaterials, i.e., Fe3O4 and DI water, due to
Direct absorption the effect of localized surface plasmon resonance; 2) the larger the concentration, the higher the solar
Hybrid nanofluid energy absorption efficiency, but the increasing rate of the absorption efficiency slows down gradually
Absorption efficiency with the increase of the concentration; 3) a numerical method to predict photothermal conversion ef-
ficiency of nanofluid under solar radiation has been proposed; 4) the novel idea of employing hybrid
nanofluid to enhance the solar absorption performance has been experimentally and numerical vali-
dated, which can enhance the solar photothermal conversion when mixing two nanofluids with different
absorption peaks, and there is an optimal mixing volume fraction for hybrid nanofluid.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction enhance the solar photothermal conversion performance,

nanoparticle-based direct absorption concept has been proposed,
With the rapid development of social economy and growth of which makes use of nanoparticles dispersed in the base fluid to
world population, there is a growing demand on energy for today's realize effective and efficient solar photothermal conversion, and
world. At the same time, with diminishing availability of fossil fuels the solar thermal energy is eventually stored in the base fluid
and increasing concerns on environmental pollution and global through the heat transfer between the nanoparticles and the base
warming, to develop sustainable and renewable energy technolo- fluid [4e6].
gies, especially solar energy related, becomes extremely important Comparing to traditional solar thermal collectors that absorb
in securing our energy future [1e3], which attracts the interests of the solar energy first by an engineered solid surface, then transport
many researchers worldwide. it through the conduction and convection processes, in this novel
However nowadays, the solar energy utilization efficiency is still concept, properly selected nanoparticles absorb the solar energy
relatively low, and there exist many challenges to overcome before directly within the base fluid. Such an idea transfers the surface
realizing its efficient and widespread utilization. While for the solar heat transfer limitation associated with conventional solar thermal
thermal energy applications, the big challenge lies in the solar collectors into volumetric absorption process, which can increase
photothermal conversion efficiency. In recent decades, in order to the solar energy absorption efficiency considerably by properly
engineering the solar absorption spectrum at the nanoscale [7e14].
So far, big progress has been made in this area since this new
concept was first proposed, and the solar energy absorption per-
* Corresponding author.
E-mail address: [email protected] (H. Jin).
formance of a variety of nanomaterials has been investigated both

https://doi.org/10.1016/j.renene.2019.04.016
0960-1481/© 2019 Elsevier Ltd. All rights reserved.
938 X. Jin et al. / Renewable Energy 141 (2019) 937e949

Nomenclature s scattering coefficient (m
1 ) Stefan-Boltzmann

constant ¼ 5:670  10
8 ðW=ðm2 ,K4 ÞÞ
A surface area exposed to solar radiation (m2) r density (kg/m3)
absorbance (
) jn spherical Bessel function of order n
an Mie coefficient to compute the amplitudes of the xn spherical Bessel function of order n
scattered field (
)
bn Mie coefficient to compute the amplitudes of the Superscripts
scattered field (
) e average value
c specific heat capacity (J=ðkg,KÞ ) / vector quantity
cp specific heat capacity at constant pressure (J=ðkg,KÞ)
D particle diameter (m ) Subscripts
Dp Petri dish diameter (m ) abs absorption
E spectral emissive power (W=m3 ) amb ambient
fv volume concentration (
) b black body
I radiative intensity (W=m2 ) ext extinction
k thermal conductivity (W=ðm,KÞ) f fluid
kf imaginary part of the complex refractive index of the h wavelength range
based fluid (
) I radiative intensity
L optical depth (m ) n nanoparticle
m mass (kg ) relative refractive index (
) p particle
n complex refractive index (
) order of accuracy sca scattering
s scattering
q heat flux (W=m2 )
w water
Q efficiency factor for Mie scattering (
)
T temperature (+ C )
Abbreviations
t time (s )
ABE absorption efficiency
U uncertainty (
)
DASC direct absorption solar collector
x characteristic size of nanoparticles (
)
DI deionized
PTE photothermal conversion efficiency
Greek symbols
RTE radiative transfer equation
b extinction coefficient (m
1 ) SAR specific absorption rate
ε spectral emissivity (
) TC thermocouple
h efficiency (
) SEM scanning electron microscope
k absorption coefficient (m
1 ) UV ultraviolet
l wavelength of light in vacuum (m)

experimentally and theoretically, which will be reviewed in brief showed that GNP has the best photo-thermal conversion capability
below. comparing to other reported nanomaterials. At the lowest particle
Otanicar et al. [15] compared the photo-thermal efficiencies of concentration examined (i.e. 0.15 ppm), GNP increased the photo-
different nanofluids including carbon nanotubes, graphite and sil- thermal conversion efficiency of the base fluid by 20% and
ver nanofluids. It is found that the optical absorption properties are reached a specific absorption rate (SAR) of 10 kW/g. The photo-
affected by the nanoparticle material, structure, shape, size and thermal conversion efficiency increased with increasing particle
volume fraction. An efficiency improvement of up to 5% in solar concentration, but the SAR showed a reverse trend. Filho et al. [18]
thermal collectors by using nanofluids as the absorption mecha- investigated experimentally the photo-thermal conversion char-
nism was experimentally demonstrated. Karami et al. [16] prepared acteristics of one of the plasmonic nanoparticles, i.e. silver, under
alkaline functionalized carbon nanotubes (f-CNT)/water nanofluid realistic conditions. Stable silver nanofluids were formulated
as working fluid of low-temperature direct absorption solar col- through a high-pressure homogenizer, and the experiments were
lector, and characterized its dispersion stability, optical properties conducted continuously under sunlight on a rooftop for 10 h. The
and thermal conductivity. Experimental results confirmed that f- results showed that silver nanoparticles had excellent photo-
CNT can raise the optical properties of the fluid due to improvement thermal conversion capability even under very low concentra-
of the light extinction level even at low volume fractions. 150 ppm tions. Up to 144% enhancement in the stored thermal energy can be
f-CNT increased the extinction coefficient of pure water by about obtained at the peak temperature for a particle concentration of
4.1 cm
1. Significant enhancement of thermal conductivity (32.2%) 6.5 ppm. Nearly constant initial specific absorption rate (SAR),
was observed for 150 ppm f-CNT/water nanofluid. With these 0.6 kW/g, was obtained for nanoparticle concentrations up to
promising properties, this kind of nanofluid is very suitable for 6.5 ppm, but it decreased significantly at higher concentrations. He
increasing the overall efficiency of direct absorption solar collec- et al. [19] prepared CueH2O nanofluids through the two-step
tors. Zhang et al. [17] proposed and validated a novel idea of using method, and the transmittance of nanofluids over solar spectrum
plasmonic nanoparticles (PNP) to improve the solar photo-thermal (250e2500 nm) was measured by the UV-Vis-NIR spectropho-
conversion efficiency. Gold nanoparticle (GNP) was synthesized tometer based on integrating sphere principle. The factors influ-
through an improved citrate-reduction method, which was used as encing transmittance of nanofluids, such as particle size, mass
an example to illustrate the photo-thermal conversion character- fraction and optical path were investigated. The extinction co-
istics of PNPs under a solar simulator. The experimental results efficients measured experimentally were compared with the
 X. Jin et al. / Renewable Energy 141 (2019) 937e949 939

theoretical calculation. Meanwhile, the photo-thermal properties absorption efficiency, it is necessary to improve the solar absorp-
of nanofluids were also investigated. The experimental results tion in the whole solar spectrum, and the application of hybrid
showed that the transmittance of CueH2O nanofluids was much nanofluids, i.e. a mixture of different kinds of nanoparticles with
less than that of deionized water, and decreased with increasing the solar absorption peak at different wavelengths dispersed into
nanoparticle size, mass fraction and optical depth. The highest the base fluid, is a practically feasible method. For instance, Au
temperature of CueH2O nanofluids (0.1 wt%) can increased up to nanoparticles have excellent solar absorption performance due to
25.3% compared with deionized water. The good absorption ability the effect of localized surface plasmon resonance, however, the
of CueH2O nanofluids for solar energy indicated that it is suitable wavelength corresponds to its solar absorption peak is around
for direct absorption solar thermal energy systems. Khullar et al. 520 nm, and its absorption capability becomes much worse when
[20] conducted an experimental study which quantitatively the solar wavelength is larger than 600 nm. For Cu nanoparticles,
compared a nanofluid-based volumetric system to a conventional the wavelength corresponds to its solar absorption peak is larger
surface absorption-based system employing a solar selective sur- than 700 nm, so it is expected to improve the solar absorption in
face. The nanoparticle dispersions were amorphous carbon nano- the whole solar visible spectrum (390e760 nm) by the application
particles dispersed in ethylene glycol and multi-walled carbon of Cu þ Au hybrid nanofluids. In this paper, hybrid nanofluids of
nanotubes (MWCNTs) dispersed in distilled water. The study Fe3O4, Cu and Au were prepared and tested under solar simulator.
showed that the nanofluid-based volumetric absorption system The photothermal conversion efficiency was evaluated based on
could be more efficient. There was an optimum volume fraction at theoretical model. Meanwhile, numerical works and other relevant
which the nanoparticle dispersion-based volumetric system per- factors affecting the solar energy absorption performance of the
formed the best. Additionally, it was also shown that higher stag- nanofluids were also investigated and discussed.
nation temperatures were possible in the case of volumetric
absorption system, which can be attributed to the cumulative effect
2. Experimental setup and material
of higher optical efficiency and the higher conversion efficiency of
radiant energy into the thermal energy in the working fluid. To
2.1. Preparation of nanofluids
assess the efficiency of direct absorption solar collector with
different nanoparticles, Zhang et al. [21] conducted an experi-
In this work, Massart co-precipitation method was considered
mental study of the photo-thermal conversion characteristics of a
for the production of Fe3O4 nanoparticles according to the
number of nanoparticle dispersions including Au, Si, Fe3O4, Al2O3
following reaction [24]:
and diamond under the same experimental setup. The results
showed that comparing with the base fluid, the introduction of
FeCl2þ 2 FeCl3þ 8NaOH/ Fe3O4þ 8NaClþ 4H2O (1)
nanoparticles can increase the photo-thermal conversion efficiency
significantly, and the efficiency increased in the order of Al2O3,
Table 1 shows the concentration and temperature condition of
diamond, (Fe3O4 and Si) and Au.
several experiment runs. The concentration of other components
Ladjevardi et al. [22] investigated the application of graphite
was prepared based on chemical stoichiometry with Ferrous
nanofluid in direct absorption solar collector by numerical simu-
chloride.
lation. Radiative transport equations along with mass, momentum
The reverse microemulsion was prepared by mixing 1 ml
and energy equations were solved together to simulate the oper-
ionized water containing FeCl3and FeCl2 with a mixture of 8 ml
ating characteristics of direct absorption solar collector. Different
cyclohexane, 0.2 g Span 80e1.8 g Tween 80 and 2 ml propyl alcohol
diameters and volume fractions of graphite nanoparticles were
for 1 h under magnetic stirring. One ml of sodium hydroxide so-
investigated. Moreover, for a proposed low-temperature solar col-
lution as the precursor was added drop wise to the reverse
lector, increase in outlet temperature, convective thermal losses,
microemulsion during 10 min. The mixture was stirred over 4 h to
and costs were evaluated. Results of this study showed that by
reach the equilibrium. A trial was performed without using any
using graphite nanofluid with a volume fraction around 0.000025%,
surfactant in the mixture to compare with the reverse micro-
it would be possible to absorb more than 50% of incident irradiation
emulsion method. SEM image for Fe3O4 nanoparticles is shown in
energy by just about 0.0045 $/L increase in cost, while pure water
Fig. 1.
solar collector can only absorb around 27% of incident irradiation
The Cu nanofluid was formulated through two step method, i.e.
energy. Luo et al. [23] established a simulation model of nanofluid
by dispersing a certain amount of commercial Cu nanoparticles into
solar collector based on direct absorption concept by solving the
DI water with pre-determined volume. In this work, the Cu nano-
radiative transfer equations of particulate media and combining
particles were purchased from the Sigma-Aldrich Corporation with
conduction and convection heat transfer equations. The system
a size range of 60e80 nm. In the preparation process, a certain
efficiency and temperature distribution were analyzed by consid-
amount of dispersing agent (tri-sodium citrate) was first blended
ering the absorption and scattering of nanoparticles and the ab-
with DI water, then the pH value of the tri-sodium citrate aqueous
sorption of the matrix. The simulation results showed that the
solution was adjusted to about 10.0 by the precise addition of NaOH
nanofluids improved the outlet temperature and the efficiency by
solution. After that, a certain amount of Cu nanoparticles was
30e100 K and by 2e25% than the base fluid. The photo-thermal
blended with the tri-sodium citrate aqueous solution. The
efficiency of 0.01% graphite nanofluid was 122.7% of that of a
coating absorbing collector. The study indicated that nanofluids,
even of very low content, had good absorption of solar radiation, Table 1
and can improve the outlet temperature and system efficiency. The condition of nanoparticle synthesis in different experiment runs.
According to the review above, both theoretical and experi- Experimental run number Ferrous chloride molarity Temperature
mental studies confirm that the employment of nanoparticles can
1 0.01 22  C (Room)
indeed enhance the absorption efficiency of solar thermal energy 2 0.05 22  C
considerably based on the direct absorption concept. Currently, in 3 0.1 22  C
most studies, only a single kind of nanoparticles was adopted. For 4 0.01 70  C
each kind of nanoparticles, it only has strong absorption capability 5 0.05 70  C
6 0.1 70  C
within a narrow solar spectrum. In order to further enhance the
940 X. Jin et al. / Renewable Energy 141 (2019) 937e949

Fe3O4 Cu Au

Fe3O4+Cu Fe3O4+Au Cu+Au

Fe3O4+Cu+Au Fe3O4, Cu, Au, Fe3O4+Cu, Fe3O4+Au, Cu+Au, Fe3O4+Cu+Au

Fig. 1. SEM images and photo of different nanofluids.

suspensions were stirred for 30 min by magnetic stirring apparatus nanoparticles is around 20e30 nm.
and then sonicated for 30 min with an ultrasonic device. SEM image The synthesized nanofluids were put into an ultrasonic bath
for Cu nanoparticles is shown in Fig. 1. (ThermoFisher Scientific, FB11207) for 30 min. The concentration of
The Au nanofluid was formulated through simultaneous pro- the original nanofluid was determined as 330 ppm, 25 ppm and
duction and dispersion of the nanoparticles in situ, i.e. one step 1500 ppm by the Atomic Absorption Spectroscopy (AAS), and the
method. Au nanoparticles were synthesized by the citrate reduc- nanofluids with different concentrations were prepared by diluting
tion method with the aid of magnetic stirring. In the synthesis the original ones with DI water. The Fe3O4, Cu and Au nanofluid
process, a mixture of 50 ml 5 mM HAuCl4 aqueous solution and with concentration of 200 ppm, 50 ppm and 6 ppm were selected
50 ml 10 mM tri-sodium citrate aqueous solution was heated until for hybrid nanofluid preparation. The diluted solutions were pro-
boiling, and stirred by a magnetic blender. The pH value of the cessed by an Ultrasonic Cell Disruption (UCD) System (Thermo-
mixture was adjusted as 7.50 by the addition of NaOH solution with Fisher Scientific, FB705) with 50% power for 2 h. After that, the
the concentration of 1.0 M, and the production process lasted about nanofluids were standing for 2 months and tested by a UV-
3 h until the color of the solution changed to dark wine red. After spectrophotometer (Shimadzu UV-1800) to compare the changes
that, Au nanofluid was purified by the membrane dialysis method. in absorption. The difference of absorbance before and after
In this process, Au nanofluid was put in a membrane tube with pore standing for 2 months was less than 1%, which indicated that the
size of 2e3 nm in diameter, which allows the smooth diffusion of nanofluids maintained good stability. The diluted Fe3O4, Cu and Au
ions but keeps the Au nanoparticles always inside the tube. The nanofluids (with concentration of 200 ppm, 50 ppm and 6 ppm,
membrane tube was located in a beaker filled with DI water of respectively) were mixed by the same volume of each one and
2000 ml and stirred by a magnetic stirrer. SEM image for gold processed by the UCD system for 3 h. The SEM images can be seen
nanoparticles is shown in Fig. 1, which clearly shows the in Fig. 1. The Fe3O4þCu, Fe3O4þAu, Cu þ Au and Fe3O4þCu þ Au
morphology information: most of the Au nanoparticles with hybrid nanofluids were tested by the UV-spectrophotometer, and
smaller sizes are spherical, while a majority of Au nanoparticles the results showed that the deviation of absorbance maintained 1%
with larger sizes are oval, and the average size of the Au in 1 week. In our previous research [13,25], adding surfactant can
 X. Jin et al. / Renewable Energy 141 (2019) 937e949 941

significantly improve the stability of nanofluid. In order to improve (Newport Co. Oriel Xenon Arc lamp, Model 94023A) was employed
the stability, dispersing agents of trisodium citrate (TSC) aqueous to simulate the real solar radiation. It provides a close spectral
solution 0.5 M and Gum-Arabic (GA) powder were added to the match to the real solar spectra. The performance parameters of the
hybrid nanofluids at 2 vol% and 0.5 wt %, respectively. The deviation solar simulator are based on the ASTM standard (ASTM E927-05),
of absorbance maintained 1% in 3 months. However, to avoid the including spectral match, non-uniformity of irradiance (5%
influence of surfactant on the absorption of solar energy, the hybrid maximum) and temporal instability (0.5% and 2.0% maximum for
nanofluids after UCD treatment and without any surfactant were short- and long-term measurements, respectively). To minimize
selected for further experiments, and the experiments were con- the temperature gradient inside the fluid, a thin layer of sample
ducted within 1 week after the UCD treatment. The optical property fluid (3 mm) was injected into a Petri dish with 3.5 cm diameter,
of nanofluid was characterized by a UV-spectrophotometer, as which was located on the bottom of an upside-down beaker in the
shown in Fig. 2. The Fe3O4 exhibits strong absorption from 300 nm center spot of the solar simulator. The solar radiation was main-
to 450 nm, and no peak absorption is found. The peak absorption of tained at approximately 980 W/m2 (1.5AM) in all the experiments,
Cu nanofluid is around 750 nm in spectrum. There is peak ab- and a uniform radiation from the solar simulator can be assumed.
sorption at the wavelength of around 530 nm for Au nanofluid with The center sample temperature was measured by a type K ther-
concentration of 6 ppm, which is due to the strong Surface Plasma mocouple (Sigma Cooperation, with uncertainty of ±0.1  C), whose
Resonance (SPR) effect in visible spectrum [26]. Many previous head was fixed on the bottom center of the Petri dish. The radiative
researches conclude that the strong absorption in visible light is the intensity of solar simulator was measured by a radiative sensor
reason why gold nanofluid has high photothermal conversion ef- (AccuPRO XP-2000) with a measurement uncertainty of 2.0%. The
ficiency. And seeking for nanofluid whose absorption shape in mass of nanofluid was measured by a digital balance (Ohaus Dis-
spectrum is similar with the shape of solar spectrum becomes covery Model DV214c) with precision of ±0.0005 g. The inner
popular when considering solar thermal harvesting [27,28]. How- diameter of the Petri dish was measure by micrometer with pre-
ever, the solar spectra emissive power exists from 200 nm to cision of ±5mm. The data was recorded in a PC though a data
3000 nm approximately, as shown in Fig. 5. Unilaterally considering acquisition hardware (thermocouple input devices, NI, USB-9211, 4-
the visible spectrum only may cause significant issues in calculating Channel, 24-bit) under the Labview environment. Preliminary tests
photothermal conversion efficiency. According to the Maxwell's with five thermocouples located at different positions on the bot-
equation [29], the scattering of nanofluid in this paper should be tom of the Petri dish showed that the space variation of the sample
independent. As Cu and Au nanofluid have peak absorption in temperature was very small, i.e. within 0.2  C. The temperature
different wavelength of spectrum, the mixing of Cu and Au nano- variation of the thermocouple during the switch on period of the
fluid makes the absorption more smooth in spectrum, as shown in solar simulator was not detected, which indicated that the solar
Fig. 2. However, the mixing of Cu an Au nanofluid will dilute each radiation didn't affect on the temperature acquiring inside nano-
other as the volume is the same. According to Beer's law [29], the fluid by the thermocouple. Sample fluid was injected slowly
absorbance of hybrid CuþAu nanofluid should be the half of through a variable volume pipette into the Petri dish before each
ACu þ AAu (A is the absorbance). That's the reason why the curve experiment.
absorbance of CuþAu nanofluid passes through the curve inter- The experiment was conducted for three cases, as shown in
section of Cu and Au. The situation is the same for Fe3O4 þ Cu and Fig. 4. For case 1, the Petri dish was covered by a glass plate (made of
Fe3O4þAu hybrid nanofluids. Further investigation into the absor- quartz glass, material type of JGS1, GiAi Photonics Corporation),
bance will be discussed in Section 4.5. which had high transparency from 185 nm to 2800 nm in spectrum.
A piece of white paper was sandwiched between the Petri dish and
the beaker; for case 2, the Petri dish was directly open to the
2.2. Experimental setup ambient, and a piece of white paper was sandwiched between the
Petri dish and the beaker; and for case 3, the Petri dish was covered
Fig. 3 shows the experimental setup. In order to minimize the by a glass plate, the white paper was removed, and a piece of black
experimental uncertainties under direct sunlight, a solar simulator foam sponge was placed in the beaker to absorb the solar light
transmitted through the sample fluid.
1.5
Fe3O4
Cu 3. Numerical model
Au
Fe3O4+Cu
Fe3O4+Au
Aiming to investigate special absorbing properties for individual
Cu+Au type and hybrids of nanofluids, a simulative model was built to
1.0 predict the Absorption Efficiency (ABE). Through numerical model,
Absorbance

Fe3O4+Cu+Au
the reason why hybrid nanofluids can enhance photothermal
conversion efficiency and how to mix hybrid nanofluids properly
can be comprehensively explained. Here we preferred to employ
realistic solar irradiation profile based on ASTM G173-03 Reference
0.5 Spectra [30], as shown in Fig. 5. Solar radiative power takes part of
more than 95% in wavelength range between 200 and 3000 nm, but
radiative power from nanofluids is mainly beyond 3000 nm, and is
much small than that of sun, as can be seen in inset. So we separate
the spectrum into two bands from 3000 nm in order to simplify
simulative model [31].
0.0
300 400 500 600 700 800 900 1000
Wavelength (nm) 3.1. Mie scattering theory

Fig. 2. The absorbance of different nanofluids. In the present modeling, the characteristic size employed in
942 X. Jin et al. / Renewable Energy 141 (2019) 937e949

Solar simulator

Sample
Power supply

Data acquisition
Fig. 3. Schematic of the experimental setup.

Solar radiation Solar radiation Solar radiation

Glass cover Glass cover

Petri dish Sample fluid Petri dish Sample fluid Petri dish Sample fluid
White paper White paper

Beaker Beaker Beaker

Black sponge

Case 1 Case 2 Case 3

Fig. 4. Three cases in the experiment.

2.5 radiative transfer equation is asxl ¼ pD=l, where D represents the

ETR
Spectral emissive power (W/(m2 nm))

Global tilt
diameter of nanoparticles. Since the diameter of suspended parti-
Direct+circumsolar cles in the experiments are much smaller than the wavelength of
2.0 1x105 0.10 irradiation (xl ≪1), it is appropriate to use simplified equations, i.e.,

8x104
A B 0.08
the Rayleigh scattering approximation [32] to calculate the ab-
sorption coefficient for nanofluids with small particle inside.
1.5 6x10 4
0.06 However, in order to obtain detailed scattering parameters, such as
the efficiencies for scattering, absorption, backscattering, averaged
4x104 0.04 absolute-square E-field, the original Mie scattering equations [29]
1.0 4
is preferred to identify the optical properties for spherical nano-
2x10 0.02
particle suspensions. The Mie scattering equations can be described
0 0.00 by:
0 3000 6000 9000 12000
0.5
Wavelength(nm)
mjn ðmxÞj0n ðxÞ
jn ðxÞj0n ðmxÞ
an ¼ 0 (2)
0.0
mjn ðmxÞxn ðxÞ
xn ðxÞj0n ðmxÞ
500 1000 1500 2000 2500 3000
ASTM G173-03 Reference Spectra Derived from SMARTS (nm)

Fig. 5. ASTM G173-03 Reference Solar Spectra Emissive Power with wavelength, inset
shows calculated spectral emissive power for sun (T ¼ 5762 K) and nanofluid jn ðmxÞj0n ðxÞ
mjn ðxÞj0n ðmxÞ
bn ¼ (3)
(T ¼ 303 K), where spectral distribution is separated into two bands, A (l < 3000 nm) jn ðmxÞx0n ðxÞ
mxn ðxÞj0n ðmxÞ
and B (l > 3000 nm).
 X. Jin et al. / Renewable Energy 141 (2019) 937e949 943

h i 2.5
2 X∞
Qsca ðlÞ ¼ 2
ð2n þ 1Þ jan j2 þ jbn j2 (4) Experiment DI water
x n¼1 Experiment 3 ppm
2.0 Experiment 6 ppm
Experiment 9 ppm
2 X
∞
Qext ðlÞ ¼ 2 ð2n þ 1ÞReðan þ bn Þ (5) Experiment 12 ppm

Absorbance
x n¼1 Experiment 15 ppm
1.5 Simulation DI water
Simulation 3 ppm
where the functions jn ðxÞ and xn ðxÞ are spherical Bessel functions Simulation 6 ppm
[29] of order n (n ¼ 1, 2,..) and the primes refer to the derivatives Simulation 9 ppm
with respect to the argument, and m represents the ratio of 1.0 Simulation 12 ppm
Simulation 15 ppm
refractive indexes, calculated by:

nparticles
m¼ (6) 0.5
nfluid

where nparticles and nfluid are the complex refractive index [33e35] of 0.0
particle material and based fluid (i.e. water) relative to the ambient 400 600 800 1000
medium, respectively. In consideration of relative low concentra-
tions of nanofluids developed for solar thermal applications, par- Wavelength (nm)
ticles should absorb and scatter light independently according to
Fig. 6. Absorbance from UV spectral-photometer and simulation for gold nanofluids of
the scattering map [29]. With such a consideration, the absorption different concentrations.
coefficient can be calculated from the below equation:
shown in Fig. 7. The total absorption efficiency (ABE) can be
3 fv Qabs ðlÞ 4pkf ðlÞ
kðlÞ ¼ kp ðlÞ þ kf ðlÞ ¼ þ (7) described as [31]:
2 D l
Here the particle of hybrid nanofluids we intend to investigate is ð 3mm  
in independent-scattering range [29], the absorption coefficient of
AðlÞLL
E0 ðlÞ 1
10 0 dl
hybrid nanofluids can be assumed as the summation of absorption 0:2mm
of each kind of nanoparticles and the based fluid, which can be hðL; fv Þ ¼ ð 3mm
expressed as: E0 ðlÞdl
0:2mm
ð 3mm  
khybrid ðlÞ ¼ kFe3 O4 ðlÞ þ kCu ðlÞ þ kAu ðlÞ þ kf ðlÞ
       E0 ðlÞ 1
e
kðl;fv ÞL dl
3 fv Qabs ðlÞ fv Qabs ðlÞ fv Qabs ðlÞ 4pkf ðlÞ ¼
0:2mm
ð 3mm (10)
¼ þ þ þ
2 D Fe3 O4 D Cu D Au l E0 ðlÞdl
0:2mm
(8)

where the superscripts represent each type of nanofluids. where the spectral wavelength for calculation is between 200 nm
Based on Beer-Lambert Law [31], the absorbance can be ob- and 3000 nm, in which most of solar energy exists.
tained as: Fe3O4, Cu and Au nanofluids with concentrations of 200 ppm,
50 ppm and 6 ppm were dispersed into each other with the same
kðlÞ,L,log10 e ¼ AðlÞ (9) volume, respectively. The absorbance for each nanofluids and
different hybrids can be seen in Fig. 2. These nanoparticle in such
Fig. 6 shows the comparison of simulative and experimental
absorption from UV-spectrophotometer. As can be seen, results
from Mie scattering theory are comparable with that from experi-
ments. All samples exhibit very similar absorption curve shapes.
The wavelength corresponds to the absorption peak is all about
520 nm, which is independent on the concentration of the nano-
fluids. Meanwhile the UV/Vis absorbance of Au nanofluids agrees
pretty well with the Beer's law, i.e. the absorbance exhibits strict
linear relation with the concentration. The proposed model can
predict the absorbance for Fe3O4 and Cu nanofluid. However, due to Reflection
the reactants and surfactant inside the fluid, the absorbance in UV
region shows some infinity values (as shown in Fig. 2), which is not
caused by nanoparticles. In this case, the model is not suitable to
predict the absorbance in UV region. In order not to dilute the focal
point of this work, the validation for Fe3O4 and Cu nanofluid is not Absorption
presented.

3.2. Predicted absorption efficiency

Transmission
As nanoparticle-based solar receiver, the solar energy absorp-
tion of nanoparticle can be simplified as 1-D radiative transfer, as Fig. 7. Schematic absorption profiles in a nanoparticle-based solar receiver.
944 X. Jin et al. / Renewable Energy 141 (2019) 937e949

low concentration nanofluids should scatter light individually, as ambient increases gradually, and the heat loss from the sample
the size compared with the wavelength is in individual scattering fluid surface to the ambient through the evaporation and convec-
range [29]. Because two different nanofluids are dispersed into tion is comparatively large. The glass cover is made of quartz glass,
each other with the same volume concentration, the absorbance which has high transparency from 185 nm to 2800 nm in spectrum.
line in the whole spectrum of UV-spectrophotometer should go The glass cover will not affect the solar radiation. However, the
through the cross point of two individual absorbance lines (i.e. the glass cover will significantly absorb the long IR radiation form the
absorbance lines for Cu, Au and CueAu hybrid nanofluids go nanofluid (above 4000 nm with the temperature of 303 K, as shown
through the same point at wavelength around 600 nm, as can be in Fig. 5), which prevents the radiative loss of nanofluid, the same
seen in Fig. 2), which is in consistent with Beer's Law. Hybrid phenomenon as the greenhouse effect. In order to avoid the in-
nanofluid has the characteristics of mixed ingredients in absor- fluence of radiative and convective heat loss on the analysis of
bance, i.e., Au nanofluid and Cu nanofluid have absorbing peaks photothermal conversion efficiency, the glass cover is necessary for
around 530 nm and 750 nm in wavelength, respectively. Obviously, further experiment. By the employment of a glass cover, the heat
hybrid nanofluid from Au and Cu has two identical peaks and ex- loss to the ambient can be effectively inhibited, and it is very
hibits more flat absorbance curve than that of Au or Cu nanofluid. necessary to seal the sample fluid in later experiments to enhance
the solar absorption performance.
4. Results and discussion As shown in Fig. 8, for a fixed solar radiation time of 220s in the
same case, i.e., case 1 or 3, the temperature rise of Au nanofluid is
4.1. Effect of test conditions on solar energy absorption performance obviously larger than that of DI water, due to enhanced solar
photothermal conversion performance of Au nanoparticles. How-
The solar energy absorption performance is influenced by not ever, more interestingly the sunlight reflection plays an important
only the working fluids employed, but also the test conditions, and role in affecting the temperature rise of the sample fluid. For DI
it is very important to understand the effect of different test con- water, the temperature rise is increased by 4.1  C when a piece of
ditions in the analysis of the experimental results. In this work, the white paper is located under the Petri dish; and for Au nanofluid,
experiment was first carried out in three cases to investigate the the temperature rise is further increased by 6.0  C. That is because
cover and reflection effects on the solar energy absorption when a piece of white paper is located under the Petri dish, the
performance. sunlight penetrated through the sample fluid is reflected upwards,
Fig. 8 shows the temperature variations of DI water and Au which will be absorbed by the sample fluid for two or even more
nanofluid with a concentration of 3 ppm in different cases. For a times, resulting in a large temperature rise of the sample fluid.
fixed solar radiation time of 220s in the same case, i.e., case 1 or 2, While when the white paper is removed, and a piece of black foam
the temperature rise of Au nanofluid is obviously larger than that of sponge is placed in the beaker, the sunlight will be absorbed by the
DI water due to enhanced solar photothermal conversion perfor- sample fluid only once because most of the penetrated sun light
mance of Au nanoparticles. However, more interestingly the glass will be absorbed by the black sponge, resulting in considerably
cover plays an important role in affecting the temperature rise of reduced temperature rise of the sample fluid. To better characterize
the sample fluid. For DI water, the temperature rise is increased by the solar energy absorption performance of the nanofluids inves-
3.4  C when it is covered by a glass plate; and for Au nanofluid, the tigated here, subsequent experiments will be always conducted in
temperature rise is further increased by 4.0  C. The final tempera- case 3, i.e., the sample fluid absorbs the sunlight only once with
ture of DI water with a glass cover is even 1.5  C higher than that of minimum heat loss to the surroundings.
Au nanofluid without a glass cover, indicating that when the
sample fluid is directly exposed to the ambient, as the fluid tem- 4.2. Effect of different nanofluids on solar energy absorption
perature rises continuously due to the absorption of solar radiation, performance
the temperature difference between the sample fluid and the
Fig. 9 shows a comparison of different working fluids on the

36
3 ppm Au nanofluid, case 1 34
DI water, case 1 12 ppm Au nanofluid case 3
3 ppm Au nanofluid, case 2
34 100 ppm Cu nanofluid case 3
DI water, case 2
3 ppm Au nanofluid, case 3 32 100 ppm Fe3O4 case 3
Temperature (oC)

DI water, case 3 DI water case 3

Temperature (oC)

32
30
30
28
28

26 26

24 24
0 50 100 150 200 0 50 100 150 200 250 300
Time (s) time (s)
Fig. 8. Temperature variations of DI water and 3 ppm Au nanofluid in different cases. Fig. 9. Comparison of different nanofluids on solar energy absorption performance.
 X. Jin et al. / Renewable Energy 141 (2019) 937e949 945

solar energy absorption performance, including DI water, Fe3O4, Cu base fluid, thermal energy stored in the nanoparticles is negligible
and Au nanofluids with different concentrations. As shown in Fig. 9, owing to its low concentration and the heat capacity of the nano-
the solar energy absorption performance of Au nanofluid is the particles is usually lower than that of water. Here the total energy
best, which is much better than that of Cu nanofluid. While for input from the solar simulator is used without considering the
Fe3O4 nanofluid, the solar energy absorption performance is not reflection from the glass tube. The evaporated water will re-
favorable, which is only slightly better than that of DI water. condensate at the bottom of the glass cover, where the latent
In fact, the solar photothermal conversion performance of a heat will release. This will trap the harvested heat absorbed from
nanofluid depends on its solar spectral absorption property, which solar radiation. What's more, with the cover of the glass, the rela-
is directly influenced by the particle material, particle shape and tive humidity inside the glass cover and the Petri dish will always
morphology and the suspension concentration. Generally, the solar be saturated, which can also prevent the evaporation of nanofluid
photothermal conversion performance of a nanofluid is more or to some extent. As analyzed above, the evaporative and convective
less above that of the base fluid, i.e., DI water. That is because heat loss is relatively small due to the glass cover (compared with
nanoparticles dispersed in the water have strong absorption of case 1). It is rational not to involve the conventional definition of
sunlight and the scattering effect between nanoparticles can also absorption efficiency, the same with our previous research [31,38].
increase the optical path of photons entering the nanofluid, which Based on the standard error analysis method [39], the uncertainty
is beneficial to the capture and absorption of sunlight. for the photothermal conversion efficiency can be expressed as:
Different from non-plasmonic materials, i.e., Fe3O4, for plas-
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 2    2  2
monic materials such as Au, Ag and Cu nanoparticles, when the
Uh UT Um 2 U UI
oscillation frequency of electrons in the metal is consistent with the ¼ þ þ2 D þ (12)
incident light frequency, the plasmon resonance can be excited at h DT mw Dp I
the metal particle surface, and the absorption and scattering effects To quantify the capability of nanoparticles in absorbing solar
of sunlight can be significantly enhanced under the condition of energy, the specific absorption rate (SAR) is employed [18]:
resonance [36,37]. Therefore, at very low concentrations, the Au or
Cu nanofluid exhibits much higher temperature rise compared to
ðcw mw þ cn mn ÞDT n
Cw mw DT w
non-plasmonic materials. SAR ¼ (13)
mn DT
The uncertainty for SAR can be expressed as:
4.3. Nanoparticle concentration effect on solar energy absorption
performance sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
   
cw mw þ cn mn 2 cw mw 2
USAR ¼ UT þ (14)
Fig. 10 shows the temperature variations of Au and Cu nano- mn Dt mn Dt
fluids with different concentrations in case 3, respectively. For both
Au and Cu nanofluids, the higher the concentration, the larger the where the uncertainty of mass of nanofluid was neglected due to
temperature rise of the nanofluids. For Au nanofluid, it is in good the large difference between water mass and nanoparticle mass.
agreement with the UVeVis absorbance results shown in Fig. 6, The uncertainty analysis showed that the uncertainty of photo-
where a higher concentration corresponds to a larger solar thermal conversion efficiency and SAR were within 1%. All the ex-
absorbance. periments were performed 3 times and the results showed that the
The absorption efficiency is conventionally defined as the ratio uncertainty was within 3%.
of the internal energy increase of the fluid to the total incident solar Fig. 11 shows the variation of the solar energy absorption effi-
radiation: ciency of Au and Cu nanofluids with different concentrations in
case 3, respectively. For both Au and Cu nanofluids, the higher the
ðcw mw þ cn mn ÞDT cw mw DT concentration, the larger the solar energy absorption efficiency of
h¼ z , (11)
IADt IA Dt the nanofluids. However, the increasing rate of the absorption ef-
ficiency slows down gradually with the increase of the concentra-
where DTis the average temperature increase. Comparing with the tion of the nanofluids. This is consistent to the Beer's law where a

34 34
DI water case 3 DI water case 3
1 ppm Au nanofluid, case 3 50 ppm Cu nanofluid, case 3
3 ppm Au nanofluid, case 3 100 ppm Cu nanofluid, case 3
32 6 ppm Au nanofluid, case 3 32 150 ppm Cu nanofluid, case 3
9 ppm Au nanofluid, case 3 200 ppm Cu nanofluid, case 3
Temperature (oC)

Temperature (oC)

12 ppm Au nanofluid, case 3

15 ppm Au nanofluid, case 3
30 30

28 28

26 26

24
A 24
B
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Time (s) Time (s)
Fig. 10. Temperature variations with concentrations in case 3 of different nanofluids: (A) Au nanofluid; (B) Cu nanofluid.
946 X. Jin et al. / Renewable Energy 141 (2019) 937e949

36 600 36 24
Absorption efficiency of Au nanofluid case 3 Absorption efficiency of Cu nanofluid case 3
SAR of Au nanofluid case 3 SAR of Cu nanofluid case 3
22
Absorption efficiency (%)

Absorption efficiency (%)

32 500 32
20

SAR (W/g)

SAR (W/g)
400
28 28
18
300
24 24 16

200
14
20
A 100
20
B 12
0 2 4 6 8 10 12 14 16 0 50 100 150 200
Concentration (ppm) Concentration (ppm)

Fig. 11. Variation of solar energy absorption efficiency and SAR with different concentrations of (A) Au nanofluid and (B) Cu nanofluid.

logarithm relation exists between the transmittance and the con- and Au nanofluid, i.e., the Fe3O4þCuþAu does not have higher ab-
centration of the nanofluids. For DI water, the solar energy ab- sorption efficiency than that of individual nanofluid, as shown in
sorption efficiency is 20.3%, while it is increased up to 34.3% and Fig. 12D.
30.2% for 15.0 ppm Au nanofluid and 210 ppm Cu nanofluid Due to the localized surface plasmon resonance effect, Au
respectively, indicating that the addition of a very little amount of nanofluids exhibit excellent absorption performance of solar ther-
nanoparticles into the base fluid, i.e. water, can significantly mal energy compared to nanofluids with non-plasmonic nano-
enhance the solar energy absorption performance. materials, such as oxide nanofluids. However, for Au nanoparticles,
At the same concentration, the solar energy absorption effi- the wavelength corresponds to its solar absorption peak is around
ciency of Au nanofluid is much higher than that of Cu nanofluid. For 520 nm, as shown in Fig. 2, and its absorption capability becomes
instance, when the concentration is 10 ppm, the solar energy ab- worse for the sunlight with the wavelength larger than 600 nm. It is
sorption efficiency of Cu nanofluid is about 21%, whereas for Au possible to further enhance the absorption of sunlight with the
nanofluid, it can be increased up to 31%. This is because Au nano- wavelength larger than 600 nm by simply increasing the concen-
particles have a much stronger effect of localized surface plasmon tration of Au nanofluid; however, it is obviously not an economical
resonance compared to Cu nanoparticles, which leads to a much way, taking into account the high cost of gold material. While for Cu
better solar photothermal conversion performance. nanoparticles, the wavelength corresponds to its solar absorption
Fig. 11 also shows the variation of the SAR of Au and Cu nano- peak is larger than 700 nm, and it is a novel idea to combine Au and
particles with different concentrations in case 3, respectively. For Cu nanofluids to improve the solar absorption in the whole solar
both Au and Cu nanofluids, the SAR decreases gradually with the visible spectrum (390e760 nm), as verified by Fig. 2 where the solar
increase of the concentration; at the same time, the SAR of Au visible light absorbance is evidently enhanced by the CuþAu
nanoparticles is much higher than that of the Cu nanoparticles in hybrid nanofluid compared with Au nanofluid at the same Au
the experiments. Clearly, the SAR is proportional to the difference nanoparticle concentration. This indicates that the application of
of the temperature increase rate between the nanofluid and the the hybrid nanofluids to further enhance the solar energy absorp-
base fluid. The overall effects result in the unique variation of the tion efficiency should be a practically feasible and cost-effective
SAR of different nanoparticles. method. The same thing happens when considering about Fe3O4
and Cu nanofluid. Because they have different absorption peaks in
spectrum, the Fe3O4þCu hybrid nanofluid has higher absorption
4.4. Solar energy absorption performance of hybrid nanofluids efficiency than that of individual nanofluid. Further investigation
will be discussed in the next section.
As introduced in section 2.1, the hybrid nanofluids were pre-
pared using the same volume of Fe3O4, Cu and Au nanofluid with
concentration of 200 ppm, 50 ppm and 6 ppm, respectively. The 4.5. Efficiency enhancement from hybrid nanofluids
photothermal conversion performance of hybrid nanofluids can be
seen in Fig. 12. The temperature variations of Fe3O4þCu hybrid In order to investigate whether hybrid nanofluid can enhance
nanofluid with different concentrations are shown in Fig. 12A. The photothermal conversion efficiency, Eq. (10) was calculated with
temperature increase of Fe3O4þCu hybrid nanofluid is higher than optical depth from 0.001 m to 0.03 m for all nanofluids we tested in
that of Fe3O4 nanofluid or Cu nanofluid. The same thing happens this paper, as shown in Fig. 13.
with Cu and Au hybrid nanofluid, as shown in Fig. 12C, i.e., the Results can be concluded as:
temperature of Cu þ Au hybrid nanofluid is 31.2  C, higher that of
Cu or Au nanofluid (which are 30.36  C and 30.89  Cat 300 s, 1) Photothermal conversion efficiency increases with optical depth
respectively). The simple mixing of Fe3O4 and Cu nanofluids, or the for all nanofluids, which is in consistent with our previous
mixing of Cu and Au nanofluid can gain extra benefit when research [18,26,31,38].
absorbing solar energy. However, the temperature of Fe3O4, Au and 2) For all nanofluids, CueAu hybrid nanofluid exhibits highest ef-
Fe3O4þAu nanofluid are 29.74  C, 30.89  C and 30.47  C, respec- ficiency while Fe3O4 nanofluid exhibits lowest efficiency
tively, which means the mixing of Fe3O4 and Au nanofluid will not 3) If two nanofluids with distinct absorbing peak in spectrum, their
gain the extra benefit, as shown in Fig. 12B. Simply mixing Fe3O4, Cu hybrid nanofluid could possibly exhibit higher absorbing
 X. Jin et al. / Renewable Energy 141 (2019) 937e949 947

32 32
Fe3O4 Fe3O4
Cu Au
Temperature (oC) 30 Fe3O4+Cu (Volume 1:1) 30 Fe3O4+Au (Volume 1:1)

Temperature (oC)
28 28

26 26

24
A 24
B
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Time (s) Time (s)
32 32
Cu Fe3O4
Au Cu
Cu+Au (Volume 1:1) Au
30 30
Temperature (oC)

Temperature (oC)
Fe3O4+Cu+Au (Volume 1:1:1)

28 28

26 26

24
C 24
D
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Time (s) Time (s)

Fig. 12. Temperature variations of hybrid nanofluids in case 3.

100
Fe3O4
Cu
Au
Fe3O4+Cu
80 Fe3O4+Au
Cu+Au
Fe3O4+Cu+Au
Efficiency (%)

60
85
80.2
80
Efficiency (%)

76.2 76.9
75.4 75.5
75
40 70.7
70

65
61.2
60
20 0
Fe Cu Au Fe Fe Cu F
3O 3O 3O +A e3 O
4 4 +C 4 +A u 4 +C
u u u+
Au

0.0 0.5 1.0 1.5 2.0 2.5 3.0

Optical depth (cm)
Fig. 13. Predicted efficiency for single nanofluids and hybrids with changing optical depth, inset shows photothermal conversion efficiency when optical depth is 0.015 m.
948 X. Jin et al. / Renewable Energy 141 (2019) 937e949

efficiency when mixing with each other with equal radio than temperature distribution is closely related to the optical depth, i.e.,
that of single nanofluid, i.e., Au and Cu nanofluid have absorbing the thickness of the petri dish. Furthermore, the solar photothermal
peak around 531 nm and 750 nm, respectively, and they have conversion characteristics of each nanoparticle should be different
efficiency about 76% and 75%; after mixed with each other to at different locations especially along the thickness direction.
become a hybrid, higher efficiency as much as 80% is reached. This work has validated the novel idea of employing hybrid
The same mechanism happens with Cu and Fe3O4 nanofluids to effectively enhance the solar absorption efficiency;
4) However, if two nanofluid share similar absorbing behavior in however, it is still at the early stage of the research, i.e., only certain
spectrum (i.e., Au and Fe3O4 have higher absorbing efficiency in concentration of the Fe3O4, Cu and Au nanoparticles are mixed and
UV range but lower efficiency in near-infrared range, as can be studied experimentally. Numerical study indicates that the optimal
seen in Fig. 2), it is possible to get a lower efficiency if mixing volume fraction of nanofluid should play important roles when
them together to become a hybrid absorbing solar energy. Future studies should focus on optimization
of the concentration and volume of hybrid nanofluids in order to
If hybrid nanofluids could enhance photothermal conversion reach a trade-off between the cost effectiveness and solar absorp-
efficiency by just mixing two kind of nanofluids with different tion performance. In addition, hybrid nanofluids composed of other
advantaged absorbing peak spectrum, it is very interesting to nanoparticles such as silver, iron oxide and single or multiple-
investigate that at what volume fraction when two kinds of nano- walled carbon nanotube nanomaterials should be considered, and
fluids mixing into each other will reach the maximum absorbing different methods to synthesize more stable hybrid nanofluids
efficiency. According to Beer's Law and Eq. (9), predicted efficiency should be explored and developed. At last, for the present study, the
changing with mixing volume fraction at optical depth of 0.015 m (a nanofluids investigated are always in the quiescent condition, and
typical value) can be seen in Fig. 14. For CuþAu hybrid nanofluids, a it is of great importance to investigate the solar absorption per-
peak efficiency of 80.1% occurs when volume fraction of Au nano- formance of different nanofluids including the hybrid nanofluids
fluid is 0.516 (the volume of Au takes 51.6% in the mixed hybrid under flow condition, which is much similar to the situation in
nanofluid). As much as 76.2% of efficiency can be reached when most practical engineering applications.
volume fraction of Cu nanofluid is 0.788 in Fe3O4þCu hybrid
nanofluid. However, for Fe3O4þAu nanofluid, absorbing efficiency
increases monotonously with increasing of Au nanofluid's volume 5. Conclusions
fraction.
In the present study, the calculation of the solar photothermal In order to enhance the solar photothermal conversion perfor-
conversion efficiency h and the specific absorption rate SAR of the mance based on the direct absorption concept, Fe3O4, Cu and Au
nanofluids are conducted in a very simple way, although it can nanofluid with different concentrations and hybrid nanofluids
reasonably reflect the major variation trends of these variables. were prepared and characterized in this work. Extensive experi-
There are still some factors that should be taken into account in the ments were conducted with different nanofluids under a solar
later research. In our previous research [31,38], ununiform tem- simulator. A numerical method to predict solar absorption effi-
perature distribution was found when nanofluid under concen- ciency has been proposed to investigate the roles of nanoparticles
trated solar radiation. In this paper, the temperature distribution of for hybrid nanofluid, and important conclusions have been drawn
the nanofluid may not be very uniform, and the one-point mea- and summarized as follows:
surement of the temperature cannot precisely represent the
average temperature of the nanofluid, although the maximum 1) The test conditions significantly affect the solar absorption
temperature difference within the nanofluid should be not large for performance of the sample nanofluid by comparing the exper-
the present experimental condition. Actually, the ununiform imental results in three cases, and the test condition where the
simulated sunlight is absorbed by the sample nanofluid only
once with minimum heat loss to the surroundings is
determined;
85
2) The solar energy absorption performance of nanofluids with
plasmonic nanomaterials, i.e., Au or Cu, is much better than that
of nanofluids with non-plasmonic nanomaterials, i.e., Fe3O4 and
80
DI water, due to the effect of localized surface plasmon
resonance;
3) The larger the concentration, the higher the solar energy ab-
Efficiency (%)

75
sorption efficiency, whereas the increasing rate of the absorp-
tion efficiency slows down gradually with the increase of the
concentration;
70
4) The solar energy absorption efficiency and specific absorption
Fe3O4+Cu rate (SAR) of Au nanofluid are much larger than those of Cu
nanofluid, because the Au nanofluid has a much stronger effect
65 Fe3O4+Au
of the localized surface plasmon resonance, but the wavelengths
Cu+Au correspond to their solar absorption peaks are much different;
5) The novel idea of employing hybrid nanofluid to improve the
60
solar absorption performance has been experimentally and
0 numerically validated, which can enhance the solar photo-
0.0 0.2 0.4 0.6 0.8 1.0
thermal conversion when mixing two nanofluids with different
Volume fraction absorption peaks. There is an optimal mixing volume fraction
Fig. 14. Predicted photothermal conversion efficiency from numerical model for
for hybrid nanofluid. Further investigation should be focused on
hybrid nanofluids with changing volume fraction of mixing ingredient when optical the roles of concentration and volume of hybrids for solar
depth is 0.015 m. thermal harvesting.
 X. Jin et al. / Renewable Energy 141 (2019) 937e949 949

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