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Desalination: Antonio Politano, Gianluca Di Pro Fio, Enrica Fontananova, Vanna Sanna, Anna Cupolillo, Efrem Curcio
Desalination: Antonio Politano, Gianluca Di Pro Fio, Enrica Fontananova, Vanna Sanna, Anna Cupolillo, Efrem Curcio
Desalination
journal homepage: www.elsevier.com/locate/desal
A R T I C LE I N FO A B S T R A C T
Keywords: In recent years, Membrane Distillation (MD) has emerged either as a promising alternative or as a complement to
Membrane distillation Reverse Osmosis (RO) in seawater desalination. However, the performance of MD is significantly offset by
Thermoplasmonics temperature polarization, a phenomenon intrinsically related to water evaporation that causes the decrease of
Photothermal effects the solution temperature at the membrane surface and, ultimately, the loss of driving force. In this work, we
Surface plasmon resonance
show that temperature polarization can be withdrawn by exploiting thermal collective effects activated by the
Seawater desalination
excitation of plasmonic modes in UV-irradiated Mixed Matrix Membranes composed of silver nanoparticles (Ag
NPs) incorporated in polyvinylidene fluoride (PVDF) microporous films. For experimental tests carried out under
vacuum (VMD) and with an absorbed radiant heating power of 2.3 · 104 W/m2, best results were obtained using
PVDF membranes loaded with 25%Ag NPs. In this case, measured transmembrane fluxes to pure water and 0.5 M
NaCl solution were 32.2 and 25.7 L/m2 h, respectively, i.e. about 11- and 9- fold higher than the corresponding
values for unloaded membranes. Remarkably, energy analysis revealed that the heat generation of Ag NPs under
plasmonic resonance was able to withdrawn temperature polarization, resulting in estimated temperature po-
larization factor (TPF) values of 106.5% for 0.5 M NaCl solution.
⁎
Corresponding author.
E-mail address: [email protected] (E. Curcio).
https://doi.org/10.1016/j.desal.2018.03.006
Received 2 October 2017; Received in revised form 18 February 2018; Accepted 6 March 2018
0011-9164/ © 2018 Elsevier B.V. All rights reserved.
Please cite this article as: Politano, A., Desalination (2018), https://doi.org/10.1016/j.desal.2018.03.006
A. Politano et al. Desalination xxx (xxxx) xxx–xxx
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A. Politano et al. Desalination xxx (xxxx) xxx–xxx
ΔW
Jw =
A⋅Δt (5)
Fig. 2. Lab-scale experimental setup. (1) VMD unit; (2) feed inlet stream; (3) feed outlet stream; (4) distillate outlet stream; (5) glass window for UV irradiation.
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Table 1
Morphological and physicochemical properties of investigated PVDF membranes. The scale bar in SEM images represents 10 μm.
Membrane Morphology (SEM micrographs) Thickness (μm) Porosity (%) Pore size (μm) Contact angle (°)
†
Before VMD tests.
‡
After 6 months.
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A. Politano et al. Desalination xxx (xxxx) xxx–xxx
plasmonic effects.
close to their plasmonic resonance turned them into local nano-heaters, k 4 A⎝ πD⎠ (9)
thus determining an enhancement of the outlet feed temperature. This
where subscript “0” identifies the center of an ensemble of plasmonic
thermoplasmonic effect increased with Ag content: the highest tem-
NPs.
perature increase, i.e. ~4 °C, was detected for PVDF-25% Ag NPs
By considering a NP diameter d of 30 nm, an approximate inter-
membrane.
particle distance p of 2 · 10−7 m for PVDF-25% Ag NPs, a unit cell area
Transient transmembrane flux profiles measured over an operation
A for a NP square lattice of p2 = 4 · 10−14 m2, an irradiance I of
time of 1 h are illustrated in Fig. 5 for both pure water (panel a) and
2.3 · 104 W/m2, a diameter of the irradiated area D of 5.2 · 10−2 m, an
0.5 M NaCl solution (panel b). Vapor fluxes through unloaded PVDF are
average thermal conductivity k of 0.37 W/mK (estimated by the ar-
noticeably lesser than through MMM embedding NP fillers. Specifically,
ithmetic average between the thermal conductivity of PVDF membrane
fluxes through PVDF-25% Ag NPs, evaluated at one hour, are about
with porosity of 0.22 [3] and water), and a NP absorption cross section
nine-fold (feed: 0.5 M NaCl solution) and eleven-fold (feed: H2O)
σabs of 2 · 10−15 m2 [31], the total ΔT is estimated to be ~42 K. Under
greater with respect to the corresponding values for virgin PVDF
these assumptions, the self-contribution term ΔT0s is largely negligible
membranes.
with respect to collective effects produced by the lattice of NPs. Since
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40 40
(b)
20 20
PVDF-25%AgNPs
PVDF-20%AgNPs
PVDF-15%AgNPs
10 PVDF-25%AgNPs 10
PVDF-20%AgNPs
PVDF-15%AgNPs
PVDF-REF PVDF-REF
0 0
0 20 40 60 0 20 40 60
Time (min) Time (min)
Fig. 5. Time-dependent profile of the transmembrane flux through PVDF membranes loaded with different amounts of Ag nanofillers. PVDF-REF denotes the unloaded PVDF membrane
assumed as a reference. The feed is: (a) pure H2O; (b) 0.5 M NaCl.
Fig. 6. Steady-state behavior of the interfacial temperature (circles) and TPF (squares) as
a function of the content of Ag NPs entrapped in PVDF membranes. Feed: 0.5 M NaCl
solution.
Eqs. (8) and (9) do not take into account the cooling effect associated to
water evaporation at the membrane interface, the predicted value of ΔT
is obviously higher than the increase of bulk temperature estimated by
energy balance in the VMD unit as per Eq. (2), i.e. 23.3 K for PVDF-25%
Ag NPs operated on 0.5 M NaCl solution (see Fig. 6). However, this
theoretical approach provides a useful tool for outlining the potential-
ities of plasmonics in thermal processes occurring at solid-liquid in-
terfaces.
Fig. 7 quantitatively illustrates the different terms of the energy
balance expressed by Eq. (4). Interestingly, for tests with pure water,
data show that the plasmonic heat flux overcomes by about 1.7-fold the Fig. 7. Heat fluxes in thermoplasmonic VMD. Feed: (a) pure H2O; (b) 0.5 M NaCl solution.
heat flux associated to the evaporation through MMM, doubling for
0.5 M NaCl solution. where A is the membrane area. EE is enhanced at increasing con-
Energy efficiency (EE) provides a quantitative estimation of the centration of NPs within the membrane matrix, reaching a maximum of
percentage of the heat stream (absorbed UV radiant flux and plasmonic 32.1% and 28.1% when using pure water and 0.5 M NaCl as feed
heat flux) that is effectively used to promote water evaporation through stream, respectively (Table 3). The exceeding energy merely increases
the membrane. EE is thus defined as: the temperature of the feed outlet stream and might be recovered by
Evaporation Heat Flux Jw λA conventional heat exchanger systems or innovative salinity gradient
EE = = power technologies [32].
Total Heat Flux ̇ p (T fb, out − T fb, in ) + Jw λA
mc (10)
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30 Pure water
The stability of NPs-charged membranes is a crucial issue in water
0.5M NaCl treatment operations. In our innovative system, the release of silver
Seawater
ions and NPs in the permeate was prevented by the shielding effect of
20 the hydrophobic polymeric matrix and the peculiar VMD configuration,
in which there is not a liquid distillate contacting the membrane. Note
that the use of thermoplasmonic membranes could be also extended to a
10
wide spectrum of applications where diffusion-driven separation me-
chanisms depends on temperature, beyond seawater desalination (see
0 as an example, the reviews in Ref. [14,19]).
0 100 200 300 400 500
Time (min)
Acknowledgments
Fig. 8. Transmembrane flux of vapor through a 25% w/w Ag-NPs loaded PVDF mem-
brane. Feed typology: pure water, 0.5 M NaCl and real seawater. We thank Guillaume Baffou for helpful discussions.
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