Research Article
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Achieving High-Quality Freshwater from a Self-Sustainable
Integrated Solar Redox-Flow Desalination Device
Karthick Ramalingam, Qiang Wei, Fuming Chen,* Kaixiang Shen, Mengjun Liang,
Jinhong Dai, Xianhua Hou, Qiang Ru, Ganguli Babu, Qinyu He, and
Pulickel M. Ajayan*
Solar-assisted electrochemical desalination has offered a new energy–water
nexus technology for sustainable development in recent studies. However,
only a few reports have demonstrated insufficient photocurrent, a low salt
removal rate, and poor stability. In this study, a high-quality freshwater
level of 5–10 ppm (from an initial feed of 10 000 ppm), an enhanced salt
removal rate (217.8 µg cm−2 min−1 of NaCl), and improved cycling and
long-term stability are achieved by integrating dye-sensitized solar cells
(DSSCs) and redox-flow desalination (RFD) under light irradiation without
additional electrical energy consumption. The DSSC redox electrolyte
(I−/I3−) is circulated between the photoanode (N719/TiO2) and intermediate
electrode (graphite paper). Two DSSCs in parallel or series connections
are directly coupled to the RFD device. Overall, this hybrid system can
be used to boost photo electrochemical desalination technology. The
energy–water nexus technology will open a new route for dual-role devices
with photodesalination functions without energy consumption and
solar-to-electricity generation.
Dr. K. Ramalingam, Q. Wei, Prof. F. Chen, K. Shen, M. Liang, J. Dai,
Prof. X. Hou, Prof. Q. Ru, Prof. Q. He
Guangdong Provincial Key Laboratory of Quantum Engineering
and Quantum Materials
Guangdong Engineering Technology Research Center of Efficient Green
Energy and Environment Protection Materials
School of Physics and Telecommunication Engineering
South China Normal University
Guangzhou 510006, P. R. China
E-mail: fmchen@m.scnu.edu.cn
Dr. K. Ramalingam, Q. Wei, Prof. F. Chen, K. Shen, M. Liang, J. Dai,
Prof. X. Hou, Prof. Q. Ru, Prof. Q. He
Guangdong-Hong Kong Joint Laboratory of Quantum Matter
Frontier Research Institute for Physics
South China Normal University
Guangzhou 510006, China
Dr. G. Babu, Prof. P. M. Ajayan
Department of Materials Science and NanoEngineering
Department Chemical and Biomolecular Engineering
Department of Chemistry
Rice University
Houston, Texas 77005, USA
E-mail: ajayan@rice.edu
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/smll.202100490.
DOI: 10.1002/smll.202100490
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1. Introduction
As predicted by the International Energy
Agency, our planet faces an energy and
water crisis in the next 20 years.[1] Human
demand for energy and water continues to
increase, but the amounts produced are
insufficient to meet consumption.[2–6] The
ocean is a huge water source, and fresh-
water can be obtained by salt removal from
seawater, which can be performed via two
major commercial techniques: thermal
distillation and membrane processing.[7–14]
The thermal-based desalination techniques
include multi-stage distillation, multi-
effect distillation, and vapor compres-
sion, all of which consume tremendous
amounts of thermal energy. For example,
the total energy consumption of a multi-
stage flash evaporation process is in the
range of 50–100 kWh m−3 to achieve high-
quality water production.[8,15] This makes it
only suitable for specific areas with abun-
dant thermal energy sources. Membrane-based desalination
includes reverse osmosis and electrodialysis processes.[11,16–18]
Using these techniques can reduce energy consumption to
<10 kWh m−3 with an output water quality with a salt content of
<500 ppm.[8,19,20] In this regard, special attention has been paid
to energy and water demand by the research community.[21–24]
These issues have led to the development of a new technique
in which renewable energy and desalination technologies are
externally coupled to minimize energy consumption.[25]
In contrast to the above techniques, electrochemical desali-
nation has become a promising and versatile method that
offers dual roles of desalination and energy storage simultane-
ously.[26–34] It removes salt ions through electrode-based reac-
tions either by physical adsorption (capacitive deionization or
nonfaradaic processes) or chemical reaction processes (battery
desalination or faradaic processes). Meanwhile, the photo-
electrochemical process technology becomes a crucial part for
the environmental remediation, for instance: the process of
water splitting by photoelectrochemical method paves a new
way to reduce energy consumption.[35–37] Similarly, to achieve
a zero-energy consumption process, photoelectrochemical
desalination technology has recently been introduced.[38,39] In
addition, another concept of solar desalination has been exten-
sively studied: solar thermal desalination. In solar thermal
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desalination, thermal energy is received by solar absorbing
materials for desalination through the steam generation pro-
cess.[40–43] However, the working principle and mechanism of
the present photoelectrochemical desalination differ signifi-
cantly from those of solar thermal desalination. In this case,
the electrochemical reaction occurs by receiving solar energy
to extract salt ions from brackish water. Recently, we demon-
strated photoelectrochemical desalination using a two-electrode
configuration, and it was found to offer only low salt removal
owing to the weak photocurrent generation.[44,45] Based on the
concept mentioned above, we have enhanced the photocurrent
with a three-electrode configuration by integrating quasi-solid-
state dye-sensitized solar cells (q-DSSCs) and a redox-flow
desalination device.[46] The two devices were interconnected by
platinized graphite paper as an intermediate electrode. In this
design, the photocurrent was increased, and the photodesalina-
tion performance was improved to reach the freshwater level
(500 ppm). The integrated device plays a major role at the pre-
sent stage, which favors the development of science and tech-
nology by coupling two different devices into a single power
pack system.[47–54] However, these architectural designs provide
inadequate long-term stability, which has to be considered as a
major concern for future applications.
In this work, the electrolyte in the dye-sensitized solar cell
(DSSC) is flowable between the photoanode and the integrated
electrode. The increased distance between the photoanode
and integrating electrode can effectively prevent electrolyte
leakage. These two factors can improve photodesalination
performance and the efficient long-term stability of the solar
redox-flow desalination (SRFD) device. The present work
tends to achieve a 5 ppm water product from an initial feed of
10 000 ppm concentration with zero energy consumption of
electrical energy. Moreover, the SRFD device performance can
be controlled by modifying two DSSC cells connected in par-
allel or in series. The parallel-based SRFD device exhibited a
high salt removal rate (SRR) of up to 217.8 µg cm−2 min−1 under
short-circuit conditions, and the solar desalination capacity was
0.42 µmol J−1. The series-based SRFD device exhibited a low
SRR of 48.8 µg cm−2 min−1 while electrical energy is released at
a high operating voltage. Therefore, the present work provides
an innovative architecture for high-performance electrochem-
ical desalination with zero energy consumption or even energy
output by solar illumination.
2. Experimental Section
2.1. Materials
Fluorine-doped tin oxide (FTO) glass sheets, with a sheet resist-
ance of 7 Ω sq−1, were purchased from Shenzen Xiangcheng
Electronic Technology Co., Ltd,(China). Graphite paper with
0.2 mm thickness was purchased from Jing Long Te Tan
(Beijing, China). Anatase TiO2 (P25), poly(ethylene oxide)
(molecular weight (MW) = 100 000), poly(ethylene glycol)
(MW = 35 000), Triton-X-100, glacial acetic acid, tetratitanium
isopropoxide, titanium tetrachloride, iodine crystals (99%),
lithium iodide (>99%), 1,2-dimethyl-3-n-propylimidazo-
lium iodide (>99%), tert-butyl pyridine, guanidine thiocyanate,
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potassium ferrocyanide (98%), and potassium ferricyanide
(98%) were purchased from Aladdin Chemicals (China). Di-
tetrabutylammonium cis-bis(isothiocyanato)bis(2,2-bipyridyl-
4,4-dicarboxylato)ruthenium(II) (N719 dye) was purchased from
Merck & Co. (USA).
2.2. Photoanode Fabrication
The photoanode was fabricated according to the method
describe in a previous report.[55] FTO glasses with dimen-
sions of 2.5 cm × 5 cm were cleaned in a detergent solution,
distilled water, acetone, and ethanol in an ultrasonic bath. A
TiO2 buffer layer was deposited by spin-coating titanium(IV)
isopropoxide (98%; Sigma-Aldrich) in an acidic medium and
sintering at 450 °C for 30 min. A compact TiO2 paste was then
prepared using 0.5 g of anatase TiO2 (Degussa, P25), 0.15 g
of poly(ethylene glycol) (MW = 35 000), 0.10 g of poly(ethylene
oxide) (MW = 100 000), two drops of Triton-X-100, and 3.5 mL
of 0.1 m glacial acetic acid. The mixture was allowed to settle
for 1 h and then stirred for 24 h. The paste was coated onto
the buffer layer using the doctor blade technique and annealed
via the following steps: 150 °C for 15 min, 350 °C for 10 min,
450 °C for 15 min, and 500 °C for 30 min. A scattering TiO2
layer was grown by immersing the plates in a 40 mm TiCl4
aqueous medium at 70 °C for 30 min. Finally, the plates were
annealed at 500 °C for 60 min, allowed to cool to 70 °C, and
immersed in a 0.3 mm solution of N719 in ethanol medium
overnight. The dye-coated film was washed with absolute eth-
anol to remove any unadsorbed dye molecules.
For parallel and series connections, FTO with a dimension
of 0.3 cm × 5 cm in the middle plate was etched out by using
a combination of Zn powder and diluted HCl, as shown in
Scheme S1, Supporting Information.
2.3. Integrated and Counter Electrode Fabrication
A sheet of 2 cm × 5 cm graphite paper was washed with acetone
and water. The surface was treated by attaching adhesive tape
and then stripping it off, and the process was repeated five times.
The integrated electrode surface was decorated with platinum
by drop-casting chloroplatinic acid (5 mm) in iso-propyl alcohol
(IPA), followed by heating at 420 °C for 15 min. The platinized-
graphite paper was allowed to face the tri-iodide/iodide redox
electrolyte flow of the DSSC. The electrode maskings and their
architectures are displayed in Scheme S1, Supporting Informa-
tion, for single-, parallel-, and series-based SRFD devices.
2.4. Fabrication of the Solar Redox-Flow Desalination Device
Fabrication of the device was similar to that in our previous
report. However, further modifications were made in the pre-
sent study. In brief, the two major parts of the SRFD device
contained three electrodes (the photoanode electrode (PE),
the integrating electrode (IE), and the counter electrode (CE))
and five compartments for electrolyte flow. The five com-
partments are described as follows: i) an I3−/I− redox couple
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electrolyte flowing between the PE and the IE; ii) two compart-
ments that recirculate an [Fe(CN)6]3−/4− redox couple electrolyte
between the IE and the CE; and iii) two compartments fixed
between an [Fe(CN)6]3−/4− redox couple electrolyte containing
NaCl salt. The SRFD architecture is constructed using the fol-
lowing configuration:
3 − /4 −
PE | I3− /I− IE Fe ( CN )6  || Feed 1 || Feed 2 || Fe ( CN )6 
Each compartment was fabricated using commercial sili-
cone rubber with a thickness of 3 mm. The redox electrolyte
composition in the DSSC was prepared as follows: 0.05 m LiI,
0.03 m I2, 0.6 m 1-hexyl-3-methylimidazolium iodide, 0.1 m
guanidinium thiocyanate, and 0.5 m 4-tert-butylpyridine in
5 mL of acetonitrile were mixed and stirred for 5 h. (Note that,
as a precaution, the amber container with DSSC electrolyte
was tightly packed to avoid ambient exposure and maintained
under an ice bath during the solar desalination process.) The
RFD redox electrolyte contained equal amounts of K3[Fe(CN)6]
and K4[Fe(CN)6] with an appropriate concentration of NaCl.
2.5. Optimization of SRFD
An optimization was conducted for the RFD portion without any
changes or modifications at the DSSC part. To reveal the effect
of the RFD redox electrolyte, the solar desalination process was
performed with x mole concentrations of [Fe(CN)6]3−/4− (where
x = 40, 80, 160, and 200 mm) by maintaining a constant con-
centration of 4000 ppm of NaCl (salt feed (1 and 2): 4000 ppm).
Furthermore, the salt concentration effect was analyzed with y
mole concentrations of NaCl (where y = 4000, 8000, 10000, and
15,000 ppm) at 160 mm of [Fe(CN)6]3−/4− redox electrolyte (salt
feed (1 and 2): y moles). The [Fe(CN)6]3−/4− of redox electrolyte
and the salt stream volumes used for photodesalination were 2
and 1 mL, respectively.
For the single-cell-based SRFD, the photoanode, interme-
diate electrode, and counter electrode were masked with an
active area of 1 cm × 1 cm using a paraffin film, as displayed
in Scheme S1. For the parallel- and series-cell-based SRFD,
two photoanode active areas were masked with dimensions
of 0.7 cm × 1.5 cm, as shown in Scheme S1, Supporting
Information.
2.6. Long-Term Stability Test
The long-term stability of the SRFD device was tested as fol-
lows: The redox electrolyte and salt stream volumes used for
photodesalination were set to 20 and 10 mL, respectively. The
reproducibility of the SRFD was analyzed by I–V characteriza-
tion, electrochemical impedance spectroscopy, and UV–visible
spectroscopic techniques.
2.7. Electrochemical Characterization
All electrochemical characterizations were conducted with a
CHI760E electrochemical workstation.
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2.7.1. Three-Electrode Cyclic Voltammetry (CV)
Cyclic voltammetry was performed in a three-electrode con-
figuration, with glassy carbon as the working electrode, a
platinum mesh as the counter electrode, and a standard Ag/
AgCl electrode as reference. The tri-iodide/iodide redox elec-
trolyte comprised 10 mm LiI, 1 mm I2, and 0.1 m LiClO4 in
3 − /4 −
| CE(1) acetonitrile. Before the tests, the samples were purged with
N2 gas for 30 min. The potential was recorded between −0.5
and +1.2 V at scan rates of 5, 10, 25, 50, 100, and 200 mV s−1.
The [Fe(CN)6]3−/4− redox electrolyte was composed of 10 mm
K3[Fe(CN)6] and 10 mm K4[Fe(CN)6] in 0.1 m NaCl. Cyclic vol-
tammetry was performed with a potential window between −0.3
and +0.6 V.
2.7.2. Electrochemical Impedance Spectroscopy
Electrochemical impedance spectroscopy was conducted in
a two-electrode configuration with symmetrical platinized
graphite electrodes. A Nyquist plot was obtained for the zero-
bias measurement. The frequency range was set between
100 kHz and 10 mHz with a sinusoidal amplitude of 5 mV for
both electrolytes. Furthermore, linear sweep voltammetry was
employed to understand the electroactivity between the redox
electrolyte and the electrodes.
2.8. Photoelectrochemical Desalination
Xenon white light with an output power of 140 mW was used as
the light source to drive the photodesalination. The I−V curve
of the SRFD device was measured using an electrochemical
workstation. The photodesalination performance was tested
in: i) the short-circuit mode, where the current–time varia-
tion was recorded using an electrochemical workstation; and
ii) the constant current mode, which was recorded by a galva-
nostatic discharge program using a battery analyzer (Neware,
Shenzhen, China). The flow rate was optimized and fixed at
3 and 4 ml min−1 for the DSSC and RFD, respectively, in the
SRFD device.
3. Results and Discussion
3.1. Design and of the SRFD Device
The experimental design and architecture of the SRFD device
for a single-cell-based SRFD (with a DSSC or RFD active area
of 1 cm2) are shown in Figure 1a and Figure S1, Supporting
Information. Figure S1, Supporting Information, illustrates the
3D model of the SRFD device. Both redox couples of the elec-
trolytes in the DSSC and RFD were recirculated through the
controlled peristaltic pump. The current system was further
modified based on our previous work by introducing a liquid
electrolyte at the flow condition in the DSSC part. In our pre-
vious report, the DSSC redox electrolyte was in a quasi-solid
state, resulting in an unstable long-term test. In addition, the
electrode separation distance has been raised to 0.3 cm between
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Figure 1. a) Schematic 3D view of the SRFD device. b) Discharge photocurrent and corresponding concentration changes at zero bias (short-circuit
between the photoanode and the counter electrode). c) Photovoltage and corresponding concentration changes when a 1.5 mA discharge current is
applied. d) Photovoltage and corresponding concentration changes when discharge currents of 1.0, 1.5, 2, and 1.5 mA are applied. The effective area
was 1 cm2.

the photoanode and the intermediate electrode to enhance the
electrolyte flow in this work. The arrangement of the SRFD
and its configuration are elaborated in the Experimental Sec-
tion and Scheme S1, Supporting Information. When the SRFD
device was illuminated, the N719 dye molecules were excited,
and the photogenerated electrons get injected into an n-type
TiO2 semiconductor. Finally, the electrons are received by the
FTO, which was connected to the counter electrode of the RFD
through the external circuit. The iodide anions were oxidized
by donating electrons to the highest occupied molecular orbital
level of photoexcited N719, forming tri-iodide in the electro-
lyte. Simultaneously, the tri-iodide anions get reduced to the
iodide anion again by gaining electrons from the desalina-
tion redox medium via the intermediate electrode. The redox
reaction of ferrocyanide (ferricyanide) occurs at the respective
electrode that extracts (transfers) Na+ ions to the desalination
(salination) stream chambers through a cation exchange mem-
brane. Therefore, the photodesalination process completes
the circuit. To understand the electrochemical behavior of
the IE, cyclic voltammetry was performed in a three-electrode
configuration, and the results are shown in Figure S2, Sup-
porting Information. With an increase in the scan rate from 5
to 200 mV s−1, the peaks at oxidation and reduction potentials
exhibit positive and negative shifts, respectively, indicating
the rapid diffusion of redox couples at the electrode surfaces,
as shown in Figure S2, Supporting Information. A linear
behavior was observed for the anodic and cathodic currents
versus the square root of the scan rate, as shown in Figure
S2b,d, Supporting Information. This behavior indicates that
the diffusion-controlled process dominates the ion kinetic
mechanism in the redox reaction.
3.2. Performance of Solar Redox-Flow Desalination Device
The photodesalination tests were conducted in either the
short-circuit mode at zero bias or the constant current mode.
Figure S3, Supporting Information, shows the effect of photo-
voltaic performance at different rates of flow in the DSSC
without and with the integrated RFD device. For further details,
see the Supporting Information. Photodesalination is per-
formed for the single-cell-based device architecture, as shown
in Figure 1a. The flow in the DSSC (single cell) can deliver an
open-circuit voltage (Voc) of 0.849 V and a short-circuit current
(Isc) of 8.67 mA. The overall efficiency (η) of the flow in the
DSSC was 1.7%, as shown in Figure S4a, Supporting Informa-
tion. With the RFD combination using ferrocyanide and ferricy-
anide as the redox medium, the output power was reduced from
3.6 to 1.5 mW (Figure S4b, Supporting Information). Recent
research has shown the high performance of electrochemical
flow desalination by utilizing ferrocyanide and ferricyanide as
redox shuttles.[56–58] Figure 1b illustrates photodesalination in
the short-circuit current mode at zero bias and its corresponding
concentration changes in both salt streams. The photocurrent
discharge initiated at 5.3 mA and decreased gradually. The salt
content in the desalination stream dropped rapidly owing to
the high short-circuit current during the initial 67.6 min. After
that, the concentration declined very slowly, reaching 5 ppm. To
understand the photodesalination performance, we emphasize
two zones in the desalination curve: i) the initial concentra-
tion to the freshwater level (500 ppm); and ii) the freshwater
level (500 ppm) to the final concentration. The higher SRR of
142.2 µg cm−2 min−1 is achieved during the desalination pro-
cess from the initial concentration to 500 ppm, indicating rapid

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salt removal to obtain freshwater within 67.6 min in the short-
circuit current mode. However, it takes nearly 45 min to desalt
500 to 5 ppm with a removal rate of 10.9 µg cm−2 min−1. The
overall salt concentration effect and photodesalination param-
eters are shown in Figure S5, Supporting Information. These
results demonstrate the effectiveness of the current device as
a high-performance photodesalination device, enabling rapid
salt removal and obtaining water with ultra-low total dissolved
solids.
Before the SRFD performance test, concentration optimiza-
tion of the [Fe(CN)6]3−/4− redox electrolyte and NaCl was per-
formed to observe the maximum output power of the SRFD
device (Figures S6–S9, Supporting Information). Figure S6,
Supporting Information, shows the photovoltaic and pho-
todesalination performances with different concentrations of
[Fe(CN)6]3−/4− redox couples (40, 80, 120, and 160 mm) with an
initial feed concentration of 4000 ppm NaCl. Upon increasing
the [Fe(CN)6]3−/4− redox concentration, the photocurrent was
enhanced because of the mode of effective ion transport and
electron transport at the integrating electrode, which leads to
rapid regeneration of the photoexcited N719 dye.
High performance was obtained for the concentration of
160 mm [Fe(CN)6]3−/4−redox couple based on the output power.
Even though all four batch samples could be reduced to 5 ppm,
the SRR varied according to the photocurrent. Figure S7, Sup-
porting Information, shows the individual photodesalination
curves for various [Fe(CN)6]3−/4− concentrations. The maximum
solar desalination capacity (SDC) of 0.25 µmol J−1 was obtained
for the 160 mm sample with an SRR of 139.7 µg cm−2 min−1, as
displayed in Figure S7e,f, Supporting Information. The SRFD
photodesalination performance results with different concen-
trations of [Fe(CN)6]3−/4− redox species are tabulated in Table S1,
Supporting Information. Further investigation was performed
to explore the photodesalination performance by setting the
salt feed concentration to 4000, 8000, 10 000, and 15 000 ppm.
Figures S8a and S8b, Supporting Information, show the
photovoltaic and photodesalination performances of the SRFD
device with different salt feed concentrations. A maximum
power output of 1.6 mW can be achieved for the device with
a salt concentration of 15 000 ppm (Figure S8a, Supporting
Information). From the photodesalination performance, high-
quality freshwater (as low as 5 ppm) can be obtained for salt
feed concentrations of 4000, 8000, and 10 000 ppm, whereas
with a salt feed concentration of 15 000 ppm, only 50 ppm
can be reached. Therefore, the maximum initial feed concen-
tration of 10 000 ppm was chosen for the other studies. The
salt concentration effect on both streams and the photodesali-
nation parameters are shown in Figure S9, Supporting Infor-
mation. The SRFD device photodesalination performance
with different salt feed concentrations is tabulated in Table S2,
Supporting Information. Electrochemical impedance spectros-
copy and linear sweep voltammetry were utilized to investigate
the kinetic reactions at the electrode–electrolyte interface and
the bulk interface. Figure S10, Supporting Information, shows
the Nyquist plot of the [Fe(CN)6]3−/4− redox couple with varia-
tions in the redox species concentration within 40–160 mm and
salt concentration within 4000–15 000 ppm. The electrochemical
impedance spectroscopy setup in the two-electrode configura-
tion and 3D view of the electrolyte flow compartment are shown
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in Figure S11, Supporting Information. In Figure S10a,b, Sup-
porting Information, the salt concentration of 4000 ppm was
kept constant, and, alternatively, the 160 mm concentration of
[Fe(CN)6]3−/4− redox species was kept constant, as shown in
Figure S10c,d, Supporting Information. The series resistance
(Rs) decreased with an increase in the concentration of redox
couples and salt concentration. Note that the first semicircle
in the Nyquist plots diminishes with increasing redox species,
indicating a rapid faradaic reaction, and the bulk resistance is
further reduced. In the low-frequency range, the faradaic pro-
cess dominated the redox reaction. The linear sweep voltam-
metry (LSV) curves are shown in Figure S10, Supporting Infor-
mation. The limiting current is saturated at particular regions,
and the linear part at the middle section corresponds to the
redox polarization behavior. The limiting current increased
with increasing redox concentration and salt concentration.
Hence, ferrocyanide–ferricyanide redox couples and salt con-
tent influence the faradaic process and improve the charge
transfer, as revealed in the CV studies. Overall, in these inves-
tigations, the electrolyte optimized in the RFD part was fixed
at 160 mm [Fe(CN)6]3−/4− redox couple and 10 000 ppm of NaCl
solution.
To demonstrate the dual functions of photodesalination and
energy output, the SRFD device was operated in a constant cur-
rent mode, as shown in Figure 1c,d. Initially, an open-circuit
voltage of the SRFD device was generated at 0.93 V after illu-
mination. When a constant discharge current of 1.5 mA was
applied, the plateau of the photovoltage could be maintained
at 0.7 V and continued to decline during the salt removal pro-
cess under the driving force of light illumination. The con-
centrations in the two salt streams demonstrated excellent
linear behavior under constant current conditions, as shown
in Figure 1c. In this process, the high saline concentration of
10 000 ppm was reduced to 826 ppm after 187.2 min, and the
removal rate was 49.4 µg cm−2 min−1, which is lower than that
of the short-circuit mode (Figure 1b). To reveal the effect of
the SRFD device performance when the constant current was
increased above 1.5 mA, the photovoltage discharge was meas-
ured at 2 mA, as shown in Figure S12, Supporting Information.
Herein, the initial photovoltage dropped to 0.57 V and the final
water product obtained had 1000 ppm of NaCl, which does not
meet freshwater quality; therefore, the constant current was
fixed at 1.5 mA for all the photovoltage discharge experiments.
The rate performance was evaluated by applying different dis-
charge currents of 1, 1.5, and 2 mA step by step each for 20 min
and then returning to 1.5 mA to complete the experiment, as
shown in Figure 1d. The photovoltage dropped from 0.936 to
0.774, 0.672, and 0.540 V at applied currents of 1, 1.5, and 2 mA,
respectively. The experimental results indicate that the short-
circuit mode can deliver excellent photodesalination, whereas
the constant current mode can achieve both electrical energy
output and desalination simultaneously.
3.3. Photodischarge Desalination with DSSC Cells in a Parallel
or Series Connection
To control the SRR and the dual functions of desalination and
energy output, a parallel or series connection was established
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Figure 2. a) Schematic 3D view of the SRFD device in a parallel connection. b) Curves of the photocurrent and corresponding concentration change
in a parallel cell connection. c) Schematic 3D view of the SRFD device in a series connection. d) Curves of the photocurrent and corresponding con-
centration changes in a series connection when a 1.5 mA current is applied. The effective area of each two-cell DSSC is 1 cm2, and a single cell of the
RFD is covered with an active area of 1 cm2.
with two active cells (of 1 cm2 in area each) between the
photoanode and intermediate electrode. The intermediate
electrode was integrated into the RFD device, as shown in
Figure 2 and Figure S1, Supporting Information. The DSSCs
produced output powers of 5.7 and 2.4 mW, respectively,
for the parallel architecture device without and with RFD,
as shown in Figure S13, Supporting Information. Figure 2b
shows the photodesalination performance and the corre-
sponding concentration changes in parallel cell connections
in the short-circuit mode. In the DSSCs without and with
the RFD architecture, the short-circuit current of the I–V
curves nearly doubled owing to the parallel connection of the
DSSC (Figure S13, Supporting Information), compared with
that obtained with the single-based SRFD device (Figure S4,
Supporting Information). With this architecture, a high
photocurrent of 9.5 mA was achieved (Figure 2b). The high
saline salt concentration of 10 000 ppm was desalted down to
5 ppm, similar to that obtained by using the single-cell SRFD
device. The salt concentration changed at both streams, and
photodesalination parameters are shown in Figure S14, Sup-
porting Information. A high SRR of 209.7 µg cm−2 min−1
was obtained as the initial 10 000 ppm concentration was
reduced to that of freshwater (500 ppm) because of the
delivery of high photocurrent. The corresponding SDC was
also increased to 0.4 µmol J−1, indicating the removal of high-
level salt concentration by utilizing the light energy.
Interestingly, it took 48 min to reduce the initial 10 000 ppm
concentration to 500 ppm whereas, in the second region, it took
60.8 min to reach 5 ppm. Compared with the single cell DSSC-
based SRFD device in Figure 1b, the two-zone desalination
Small 2021, 17, 2100490
www.small-journal.com
period was reversed. This is due to the delivery of a high
photocurrent by the DSSC connected in parallel as well as in
the short-circuit mode, which causes a rapid decline in the salt
concentration.
To obtain a high energy output, the two DSSCs were con-
nected in series for photodesalination, as presented in
Figure 2c,d. In this case, the photovoltaic performance of the
DSSC reached 1.75 V and 8.3 mA with an enhanced output
power of 7.1 mW, while the photovoltaic response of SRFD
was 1.74 V and 6.1 mA (Figure S15, Supporting Information).
Among all the devices, this architecture achieved the maximum
output power (3.4 mW). The photodesalination performance
was measured under a constant current mode of 1.5 mA, as
shown in Figure 2d. The photovoltage discharge initiated at
1.45 V gradually decreased, indicating the removal of ions from
the desalination salt stream. Based on constant current-mode
photodesalination measurements, the series-connected SRFD
device exhibited excellent performance with a final concen-
tration of 23 ppm. The photodesalination performance based
on single (Figure 1c) and series-connected (Figure 2d) SRFD
devices in constant current mode is tabulated in Table S3, Sup-
porting Information. It is apparent that the series-based SRFD
device can improve photodesalination performance by oper-
ating in the constant current mode because of the higher photo-
voltage. Finally, we examined the impact of the photoelectrode
effective area by connecting DSSCs in parallel or series with an
electrode area of 1 cm2. Both devices achieved excellent photo­
desalination because of the delivery of high photocurrent by
parallel-based SRFD devices and high photovoltage by series-
based SRFD devices.
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Figure 3. Long-term tests for single, parallel, and series cells. a) Single-cell curves of the photocurrent and corresponding salt concentration changes at
zero bias. b) Parallel-cell curves of the photocurrent and corresponding salt concentration changes at zero bias. c) Series-cell curves of the photovoltage
and corresponding salt concentration changes at a 1.5 mA discharge current. d) Photovoltaic performance comparison of single, parallel, and series
solar cells before and after the long-term tests. The initial salt concentration was 10 000 ppm and the volume was 10 ml.

3.4. Long-Term Stability Tests of Single, Parallel, and
Series Connections
The long-term stability test was performed by increasing the
salt volume up to tenfold that of the previous experiments.
Figure 3 and Figure S16, Supporting Information, show the
photodesalination performance of single, parallel, and series
cells for long-term analysis. It is difficult to reach 5 ppm with
any of the devices in the long-term tests. The final concentra-
tions obtained were 24, 17, and 25 ppm for the single, parallel,
and series-based SRFD devices, respectively. The short-circuit
mode demonstrates a higher photodesalination performance
than the constant current mode because the partial energy is
output to the external circuit. Among the three types of tests,
the parallel-cell-based SRFD device exhibited the highest photo­
desalination performance. The SRR is up to 172.5 µg cm−2 min−1
with an SDC of 0.34 µmol J−1 in the parallel-based SRFD device
that is a factor of 5 greater than that of the series-based SRFD
device. However, in the series connection, electrical energy
output can also be achieved simultaneously, in addition to
photodesalination, as shown in Figure 3c. Figure 3d shows the
photovoltaic performance parameters before and after the long-
term test. There was no apparent variation in Voc and Isc after
long-term testing was completed, but an insignificant drop was
observed in the fill factor (FF). This may be due to recombina-
tion resistance loss. Moreover, the photoanode (TiO2/N719) sta-
bility was analyzed with UV–visible spectroscopy to reveal the
light absorption variation, as shown in Figure S17, Supporting
Information. The peak range between 250 and 380 nm corre-
sponds to the π–π* interaction within the bi-pyridyl complexes
of N719 dye, which did not exhibit any changes after the long-
term test. However, the peaks at 530 and 402 nm exhibit a hyp-
sochromic effect (blue shift) after the long-term test, and this
may be mainly influenced by the redox electrolyte species.[59,60]
Nevertheless, the electrochemical impedance spectra and I–V
curve still prove the stability of the photoanode after long-
term processing. The unchanged photovoltaic performance
was further confirmed by electrochemical investigation, as
shown in Figure S18, Supporting Information. The interme-
diate electrode–electrolyte and TiO2–electrolyte interfaces were
not affected after the long-term tests. Moreover, ionic diffu-
sion in the electrolyte slightly increased after long-term tests,
which may have influenced the photovoltaic performance of the
DSSC. This study highlights the importance of understanding
the long-term stability. In future work, we will focus on
enhanced interfacial engineering in the DSSC compartment.
4. Conclusion
In this work, an SRFD device was developed to achieve high-
quality water products by utilizing solar energy. I3−/I− and
[Fe(CN)6]3−/4− were allowed to flow in the DSSC and RFD indi-
vidually, separated by an intermediate electrode. Overall, the
SRFD device was optimized by varying the redox couple and
NaCl feed concentration. After the optimal investigation at the
RFD part, the redox couple [Fe(CN)6]3−/4− concentration was
fixed at 160 mm with 10 000 ppm as the NaCl feed. A high pho-
todesalination performance with an SRR of 209 µg cm−2 min−1
was achieved in the parallel-connected DSSC (two 1 cm2 cells)

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www.advancedsciencenews.com
under short-circuit conditions. Similarly, DSSCs connected in
series (two 1 cm2 cells) operated at high photovoltage discharge;
however, the photodesalination performance was not com-
parable with the short-circuit-mode operation because of the
current difference. The long-term stability of single-, parallel-,
and series-connected SRFD devices was also demonstrated by
increasing the volume of salt feed up to 10 mL. Significantly, the
photovoltaic performance of the DSSC was almost unchanged
even after the long-term tests. Therefore, the proposed SRFD
architecture provides the dual functions of both electricity gen-
eration and desalination within a single device with a solar
driving force. This is the first report of high photodesalination
that can produce 5 ppm water products. These findings demon-
strate the feasibility of utilizing sunlight energy to achieve high
desalination performance.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
K.R. and Q.W. contributed equally to this work. This project was
supported by National Key Research and Development Program of China
(2019YFE0198000), Science and Technology Program of Guangzhou
(2019050001), Scientific and Technological Plan of Guangdong Province
(2018A050506078), the Department of Education of Guangdong
Province (2019KZDXM014), National Natural Science Foundation of
China (51972122, 51672090), and SCNU Outstanding Young Scholar
Project (8S0256). Dr. R.K. thanks the post-doctorate scholarship from
South China Normal University, P. R. China. F.C. acknowledges the Pearl
River Talent Program (2019QN01L951).
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
Research data are not shared.
Keywords
energy consumption, photodesalination, photoelectrochemical
desalination, redox-flow desalination, salt removal rate
Received: January 25, 2021
Revised: April 20, 2021
Published online: June 23, 2021
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