Accepted Manuscript

Solar desalination of seawater using double-dye-modified PTFE membrane

Masahiro Fujiwara, Masaki Kikuchi

PII: S0043-1354(17)30844-8
DOI: 10.1016/j.watres.2017.10.015
Reference: WR 13272

To appear in: Water Research

Received Date: 30 June 2017

Revised Date: 21 September 2017
Accepted Date: 7 October 2017

Please cite this article as: Fujiwara, M., Kikuchi, M., Solar desalination of seawater using double-dye-
modified PTFE membrane, Water Research (2017), doi: 10.1016/j.watres.2017.10.015.

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Graphical Abstract

Solar desalination of seawater using double-dye-modified

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PTFE membrane
Masahiro Fujiwara*1 and Masaki Kikuchi1,2

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1
National Institute of Advanced Industrial Science and Technology (RICPT; Tohoku
Center), 4-2-1 Nigatake, Miyagino-ku, Sendai, Miyagi 983-8551, Japan

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Tohoku Gakuin University, 1-13-1 Chuo, Tagajo, Miyagi 985-8537, Japan

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Seawater
Solar Light
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Drain
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Freshwater
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1 Solar desalination of seawater using double-dye-modified

2 PTFE membrane

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4 Masahiro Fujiwara*1 and Masaki Kikuchi1,2

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6 National Institute of Advanced Industrial Science and Technology (RICPT; Tohoku

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7 Center), 4-2-1 Nigatake, Miyagino-ku, Sendai, Miyagi 983-8551, Japan
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8 Tohoku Gakuin University, 1-13-1 Chuo, Tagajo, Miyagi 985-8537, Japan

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9 CORRESPONDING AUTHOR FOOTNOTE: Phone +81-72-751-9253; Fax +81-22-

10 237-5224; E-mail m-fujiwara@aist.go.jp

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15 ABSTRACT

16 The production of purified water by seawater desalination is now a significant

17 countermeasure against recent severe water shortage. As the global warming is thought

18 to be a dominant cause of the water scarcity problem, the energy employed for the

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19 desalination should be free from fossil fuels. We recently reported a simple membrane

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20 desalination combining the harvesting of solar energy and the membrane permeation of

21 vaporized water. Water on a PTFE (polytetrafluoroethylene) membrane modified with

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22 disperse red 1 (DR1) as an azobenzene dye that photo-isomerizes with visible light

23 permeates through it under visible light irradiation. The penetrated water was efficiently

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desalinated to produce purified water by membrane distillation mechanism, where water
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25 was evaporated by DR1 using solar energy. In this paper, we report that the aqueous
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26 solution of rhodamine B on non modified PTFE membrane permeated the membrane to

27 be purified under visible light irradiation. This paper also reports that a PTFE membrane
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28 modified with disperse blue 14 (DB14) was active for the desalination. Thus, even these
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29 non-azobenzene dyes were revealed to be available for the light induce water

30 permeation. When DR1 and DB14 were modified to PTFE membrane concurrently, a
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31 higher performance of seawater desalination using simulated sunlight was achieved by

32 efficient absorption of the irradiated light with DR1 and DB14.

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34 Keywords: Seawater desalination; Solar energy; PTFE membrane; Dye; Disperse Blue

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39 1. INTRODUCTION

40 The purification of waste water and the desalination of seawater are now current

41 essential technologies. Especially the production of fresh water from seawater is an

42 effective solution to recent severe water shortage problem. As the huge amount of CO2

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43 emissions from fossil fuels and the resulting climate change (so-called “global

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44 warming”) are believed to be responsive for the water shortage problem (Arnell et al.,

45 1999; Gosling et al., 2016; Misra et al., 2014), the desalination driven by solar power

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46 energy, “solar desalination”, is a desired countermeasure against the problem (El-Bialy

47 et al., 2016; El-Sebaii et al., 2015; Khayet et al., 2013; Ali et al., 2011; Shatat et al.,

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2013; Li et al., 2013). The solar desalination is roughly categorized into two types based
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49 on the usage style of sunlight, i.e. direct and indirect processes (Ali et al., 2011). In the
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50 former case, sunlight is directly used as in the cases of solar still and humidification-

51 dehumidification process. In the latter case, sunlight is initially converted into heat by
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52 solar water heating or into electricity by photo-voltaic process, being used to the
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53 desalination processes such as reverse osmosis, electrodialysis, membrane distillation

54 and other processes through the heating or electricity.

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55 Recently, technologies toward zero liquid discharge (ZLD) have come to draw

56 attention, because minimizing the discharge of waste water and maximizing water reuse
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57 are desired for freshwater production (Tong et al., 2016). While reverse osmosis (RO) is

58 unsuitable for the desalination of high concentrated salt water (brine), thermal

59 evaporation processes including membrane distillation are still effective for the

60 desalination. In terms of seawater and brine desalination free from fossil fuel, solar

61 power must be employed even in these processes. The technologies of the thermal

62 evaporation by light absorbing materials that promote light-to-heat conversion are

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63 actively studied in recent years. For example, thermal evaporation of water is achieved

64 using plasmonic titanium nitride nanoparticles under light irradiation (Ishii et al., 2016).

65 A combined system of exfoliated graphite and carbon foam (Ghasemi et al., 2014) and a

66 nanoporous graphene sheet (Ito et al, 2015) are active for the water stream production as

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67 well. About membrane process, a hydrophobic membrane consisting of polypyrrole

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68 coated stainless steel mesh is claimed to be effective for water evaporation by light-to-

69 heat conversion, which is potential for seawater desalination with direct use of sunlight

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70 (Zhang et al., 2015). Bifunctional TiO2-Au-anodized alumina membrane with three

71 layers integrating photocatalytic degradation and solar water vapor generation is

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reported for the purification of contaminated water (Liu et al., 2016). The light
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73 irradiation to anodized alumina membrane with gold nanoparticles also produces water
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74 vapor that permeates upward thorough the membrane (Yu et al., 2015).

75 The application of light harvesting materials to membrane distillation is now

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76 considered as an important challenge in solar desalination. While the part to produce the
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77 warmer water by heating with sunlight are separated from the part of the membrane

78 distillation using the warmer water in the indirect use of sunlight (Fig. 1A), membranes
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79 functionalized for light harvesting integrate with those two parts to create a simple

80 membrane distillation process by the direct utilization of sunlight (Fig. 1B). A “direct-
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81 contact” membrane distillation using solar power for desalination is recently reported

82 using nano-photonic particles, where hydrophobic polyvinylidene fluoride membrane

83 for membrane distillation and hydrophilic polyvinyl alcohol one with dispersed carbon

84 black nanoparticles for light harvesting are associated (Dongare et al., 2017). In addition,

85 the direct joule heating of the interface of water and hydrophobic membrane with a

86 porous thin film carbon nanotube is claimed to be effective for seawater desalination by

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87 membrane distillation mechanism (Dudchenko et al., 2017). We also reported light

88 induced water purification processes using azobenzene dye modified membrane

89 materials (Fujiwara et al., 2015; Fujiwara, 2017). Anodized alumina membrane with a

90 grafted azobenzene substituent achieved water permeation through the membrane by the

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91 simultaneous irradiation of UV and visible light (Fujiwara et al., 2015). The concurrent

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92 irradiation of UV and visible light induces the repetitive photo isomerization of the

93 azobenzene group between its trans- and cis-form, which vaporizes the water on the

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94 membrane to promote the penetration of water vapor across the membrane. In this case,

95 the purified and desalinated water was readily recovered under the membrane (Fig. 1B).

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This process is thought to be a variation of “air-gap” membrane distillation
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97 (Meindersma et al., 2006; Koschikowski et al., 2003; Ding et al., 2005; Gude et al.,
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98 2011; Banat et al., 2007), whose key step is the transportation of vaporized water

99 formed from warmer water through hydrophobic membrane. In a subsequent paper, we

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100 reported an improved membrane process, which employed disperse red 1 (DR1) as an
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101 alternate azobenzene dye that isomerizes only with visible light and a PTFE

102 (polytetrafluoroethylene) membrane as a practical alternative for anodized alumina

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103 membrane. This DR1 modified PTFE membrane was effective for the water permeation

104 and desalination only using visible light (Fujiwara, 2017). Artificial seawater penetrated
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105 the modified PTFE membrane under visible light irradiation to produce purified and

106 desalinated water under the membrane. In this paper, we report our further examinations

107 on the light induced water permeation through PTFE membrane. As DR1 does not

108 absorb visible light of wavelength longer than 600 nm (Fujiwara, 2017), no significant

109 fractions of sunlight were utilized. The azobenzene molecules generally cause their

110 photo isomerization using UV or shorter-wavelength visible light, and for using longer-

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111 wavelength visible light dye molecules other than azobenzene derivatives are required.

112 As mentioned even in our latest paper (Fujiwara, 2017), one of our goals is the creation

113 of a simple seawater desalination process using sunlight as a principal energy source

114 (Fig. 2). Therefore, dye modified membranes that can efficiently harvest the whole

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115 sunlight energy were explored.

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116 (Figure 1)

117 (Figure 2)

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118

119 2. EXPERIMENTAL SECTION

120 2.1. Materials

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121 Polytetrafluoroethylene (PTFE) membrane used in this study was Advantec
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122 PTFE membrane filter from Toyo Roshi Kaisha, 47 mm in diameter and 3.0 µm in pore

123 size. Disperse red 1 [N-ethyl-N-(2-hydroxyethyl)-4-(4-nitrophenylazo)aniline], disperse

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124 blue 14 [1,4-Bis(methylamino)anthraquinone] and rhodamine B (Fig. 3) were obtained

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125 from Sigma-Aldrich Co. LLC. An artificial seawater was prepared by the mixing of

126 MARINE ART SF-1 (Osaka Yakken Co., Ltd.) with appropriate volume of distillated
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127 water. Other reagents were purchased from Wako Pure Chemical Industries, Ltd.
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128 (Figure 3)
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130 2.2. Preparation of dye modified membranes

131 In this study, an improved modification procedure of PTFE membrane with dyes

132 was employed. A PTFE membrane was soaked in a saturated solution of DR1, DB14 or

133 DR1+DB14 obtained as a supernatant solution of the corresponding concentrated

134 solution. After10 min, the membrane was taken from the solution to be heated at 40°C

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135 for 10 min in air. The membrane was immersed in the same solution again with flipping

136 the membrane for 10 min, and heated at 40°C for 10 min in air. These treatments were

137 repeated totally 10 times, and the resulting membrane was washed in distilled water

138 with ultrasonic cleaner for eliminate removable dye. This procedure produced well-

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139 colored PTFE membranes more than the previous one (Fujiwara, 2017).

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141 2.3. Procedures of membrane permeation of water

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142 The experiment of water permeation through membrane was carried out using

143 the same apparatus system as that used in our latest paper (Fujiwara, 2017). A

144
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membrane was put on a Teflon holding ring platform (outside diameter of 37 mm,
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145 inside diameter of 33 mm and 3 mm thickness) in a glass petri dish. A watch glass was
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146 overlaid on the petri dish. The light was irradiated onto a whole water droplet (0.5 ml)

147 on the central part of a membrane in dark place (the contact area between the droplet
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148 and the membrane was approximately 1.13 cm2). The wavelength of visible light
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149 irradiated from a xenon light source (MAX-301, 300 W xenon lamp; Asahi Spectra Co.

150 Ltd.) was controlled mainly in the range from 385 to 740 nm at approximately 850
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151 W/m2 by an attached VIS mirror module (Asahi Spectra Co. Ltd.), which effectively
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152 eliminated UV and near-infrared light. The visible light irradiations limited to shorter-
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153 wavelength and longer-wavelength were performed using a short pass filter (SVX550; <

154 550 nm) or a long pass filter (LVX550; >550 nm), respectively, obtained from Asahi

155 Spectra Co. Ltd. The irradiation of near infrared light in the range from 750 to 1050 nm

156 was performed using the xenon light source attached NIR mirror module (Asahi Spectra

157 Co. Ltd.). A simulated sunlight was irradiated from a solar simulator (Fiber Solar

158 Simulator XEF-300, SAN-EI ELECTRIC CO., LTD.) at about 1000 W/m2 (1 SUN).

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159 The energies of the irradiated lights were measured by a pyranometer (ML-01 Si-

160 pyranometer, EKO instruments).

161 After the light irradiation, the temperature of the remained water on the

162 membrane was measured with a sharpened thermocouple quickly, and the water was

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163 recovered with a syringe to estimate the volume, which were not necessarily accurate

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164 depending on the state of the water. Thermography images with or without light

165 irradiation were recorded with testo 868 thermal imager. Especially in the cases using

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166 artificial seawater, the complete recovery was difficult due to the spreading of the

167 seawater on the membrane. The volumes of the water both under the membrane (on the

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bottom of the petri dish) and above the membrane (on the undersurface of the watch
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169 glass) were measured using suitable microsyringes for HPLC. In this paper, the water
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170 under the membrane and that above the membrane are called as “permeated water” and

171 “evaporated water”, respectively. For analyzing electric conductivity, distilled water
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172 (electric conductivity: 1~3 µS/cm) was added to the permeated water for increasing the
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173 volume. The electric conductivity of the mixed water was determined by a conductance

174 meter, B-771 LAQUAtwin compact conductivity meter (HORIBA, Ltd). The estimated
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175 electric conductivity of the permeated water was corrected by the dilution ratio with the

176 additional distilled water. The electric conductivity thus calculated is the maximum
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177 value because the electric conductivity of the additional distilled water was not

178 incorporated in the calculation. In repeated desalination experiments, the artificial

179 seawater on membrane was simply replaced by the fresh seawater in respective runs

180 without washing the membrane for avoiding the removal of salts remained on the

181 membrane.

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183 2.4. Sample Characterization

184 The UV-vis spectra of dye solutions were recorded by JASCO V-530

185 spectrometer. The diffuse reflectance spectra of the membranes were analyzed with

186 Shimadzu UV-3600Plus UV-Vis-NIR spectrometer equipped with an integrating

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187 sphere, where Kubelka Munk function was used as the diffuse reflectance spectra of

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188 membranes.

189

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190 3. RESULTS AND DISCUSSION

191 3.1. Water permeation of rhodamine B aqueous solution under visible light irradiation

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At first, we ascertained the availability of non-azobenzene dye and dye-
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193 dissolving aqueous solution in the light induced water membrane permeation and water
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194 purification for the sake of expanding the usability of this process. The aqueous

195 solutions dissolving rhodamine B as a representative water soluble and non-azobenzene

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196 dye were employed for the examination. The aqueous solution of rhodamine B has the
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197 absorption of visible light from 500 to 600 nm and has the peak at about 553 nm in

198 wavelength (Fig. 4). Aqueous solutions of rhodamine B of various concentrations (0.5
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199 mL) were put on non modified PTFE membrane (as received original PTFE membrane

200 filter). Visible light of wavelength ranging from 385 to 740 nm was irradiated to the
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201 whole droplet of the purple aqueous solutions of rhodamine B. After 1 h irradiation,

202 water dews were found both on the bottom of the petri dish under the membrane

203 (“permeated water”) and on the undersurface of the watch glass above the membrane

204 (“evaporated water”). For example, in the case of 1 mM solution of rhodamine B, the

205 volumes of the permeated and evaporated water were about 20 and 8 µL, respectively.

206 The temperature of the remained solution on the membrane after the irradiation

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207 increased from 26.6 to 28.2°C. When water without rhodamine B (distilled water) was

208 used, neither permeated nor evaporated water was observed. In addition, no visible light

209 irradiation to the rhodamine solution (in dark place) resulted in no permeation and

210 evaporation of water. In these control experiments, no clear elevations of the

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211 temperature of the solution were detected. It is noteworthy that the permeated water had

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212 no color and the absence of rhodamine B was confirmed by the absorption spectra of

213 visible light. In our previous papers (Fujiwara et al., 2015; Fujiwara, 2017), the

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214 repetitive photo isomerization of azobenzene dyes by light irradiation evaporates water

215 on the membrane to promote the membrane permeation of vaporized water. However,

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rhodamine B is a non-azobenzene dye and has no property of photo isomerization. A
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217 part of the light energy absorbed in rhodamine B is used for fluorescent emission, and
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218 the rest part of the energy is released as heat. This heat causes the temperature elevation

219 of the solution, because no temperature increase occurred in water without rhodamine B
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220 as described above. The water on the PTFE membrane is evaporated by the heat from
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221 rhodamine B absorbing the irradiated light to permeate through the membrane as water

222 vapor, condensating on the petri dish to produce the purified water containing no
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223 rhodamine B. The mechanism of water penetration by water vapor formation is

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224 analogous to that of membrane distillation.

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225 (Figure 4)

226 Fig. 5 shows the plots of the volumes of the permeated and evaporated water and

227 the temperature of the remained water on the membrane after the irradiation as a

228 function of the concentration of the rhodamine B solutions. In low concentration, the

229 volumes of the permeated and evaporated water increased with the concentration of

230 rhodamine B monotonically. However, the increases of the water volumes became slow

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231 when the concentration was more than 0.2 mM, and nearly plateaued in high

232 concentration (>5 mM). The increased volumes of the permeated water in low

233 concentration indicated that rhodamine B provoked the water permeation. In these cases,

234 the temperature of the water on the membrane was also elevated. The solutions in these

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235 concentrations were pale purple and comparatively transparent. It is thought that the

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236 absorption of the irradiated visible light by rhodamine B effectively occurred near the

237 membrane to promote the evaporation and membrane penetration of water. On the other

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238 hand, the rhodamine B solutions in high concentration were dark purple and nearly

239 opaque. The irradiated light is hardly reached at the membrane by the block of the non-

240
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transparent solution. In addition, the high concentration of the dye caused the depression
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241 of vapor pressure to inhibit the evaporation of the water. Therefore, the increase of the
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242 volume of the permeated and evaporated water plateaued in the concentrated solutions.

243 The results of rhodamine B solutions revealed two important features of the light
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244 induced water permeation with dye compound, that is, the membrane permeation of
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245 water is also achieved by non-azobenzene dye and dye aqueous solution. However, the

246 dark colored dye solution was not effective due to the inhibition of the reaching of the
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247 irradiated light to the membrane. The direct modification of dye compound to the PTFE

248 membrane seems to be more preferable, because dye is located only on the surface of
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249 the membrane to harvest light energy efficiently. A key point of the process of the dye

250 modified membrane is the evaporation of water at the interface of the membrane to lead

251 the immediate permeation of vaporized water through the membrane. Then, we next

252 attempted PTFE membranes modified with a non-azobenzene dye that absorbs the long-

253 wavelength visible light.

254 (Figure 5)

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255

256 3.2. Preparation of dye modified PTFE membranes

257 In this study, we chose disperse blue 14 (DB14) as a non-azobenzene dye (Fig.

258 3). From the absorption spectra of the ethanol solutions of DR1 and DB14 illustrated in

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259 Fig. 4, DB14 efficiently absorbs visible light with wavelength longer than 600 nm,

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260 which DR1 scarcely harvests. Although some surface treatments of PTFE are generally

261 required for the grafting of organic compounds onto PTFE membrane (Liu et al., 2004;

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262 Fang et al., 2003; Youxian et al., 1991; Reznickova et al., 2011), DR1 was directly

263 embrocated onto PTFE membrane in our previous paper (Fujiwara, 2017). As the

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solubility of DR1 to water was poor, DR1 just adsorbed on the membrane hardly seeped
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265 to water. DB14 is less soluble in water than DR1, and this dye was simply embrocated
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266 on PTFE membrane as well. In this study, an improved modification method of DR1

267 and DB14 with PTFE membrane was performed. The details of the method are
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268 described in the experimental section.

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269 Fig. 6A and 6B show the images of the DR1 and DB14 modified PTFE

270 membranes by the improved modification method, respectively. The DR1 modified
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271 membrane had a deep red color, which appeared to be darker than the membrane used in

272 our previous paper (Fujiwara, 2017). The DB14 modified PTFE membrane had a rich
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273 blue color. Fig. 7 illustrates the diffuse reflectance UV-Vis-NIR spectra of these

274 modified membranes. No absorptions of dyes in the membranes were detected in

275 wavelengths longer than 1000 nm. The absorption peak of the DR1 modified PTFE

276 membrane was observed at about 500 nm in wavelength, and the absorption of visible

277 light of wavelength longer than 650 nm was low. On the other hand, the DB14 modified

278 PTFE membrane absorbed visible light of wavelength longer than 500 nm sufficiently.

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279 A PTFE membrane modified both DR1 and DB14 was also prepared using the mixed

280 acetone solution of them. The image and the diffuse reflectance spectrum of this double

281 dye (DR1 and DB14) modified membrane are also shown in Fig. 6C and Fig. 7,

282 respectively. The membrane had a dark gray color and had two peaks of the absorption

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283 at about 530 and 700 nm in wavelength. The spectrum of the double dye modified

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284 membrane appears to be well fixed to that of solar irradiance. It is expected that sunlight

285 can be effectively harvested by this membrane.

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286 (Figure 6)

287 (Figure 7)

288
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289 3.3. Light induced water permeation through dyes modified PTFE membranes
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290 As we ascertained in our previous paper (Fujiwara, 2017), neither the

291 permeation nor the evaporation of distilled water on non modified PTFE membrane
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292 occurred not only in dark place but also under visible light irradiation for 1 h. The
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293 whole volume of the water on the membrane was recovered. We also tested the natural

294 dropping-down of the water through all three dye modified PTFE membranes in dark
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295 place, and no permeated water was found under the membranes. Table 1 summarizes

296 the results of the membrane permeation of distilled water under visible light irradiation.
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297 When the DR1 modified PTFE membrane was used in the light induce experiment

298 where visible light ranging from 385 to 740 nm was irradiated for 0.5 h, 23 µL of the

299 permeated water was recovered on the petri dish under the membrane. About 8 µL of

300 the evaporated water was also found on the undersurface of the watch glass above the

301 membrane. Although the previous paper has already reported the water permeation

302 using a different DR1 modified PTFE membrane (Fujiwara, 2017), the DR1 modified

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303 membrane prepared by the improved method was more active than the previous one

304 probably because of much more modification of DR1, which was understandable from

305 the color strength of the membranes. The DB14 modified PTFE membrane was also

306 active for the water permeation. About 28 µL of the permeated water was found under

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307 the membrane. This membrane had a higher ability than the DR1 modified one. Thus,

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308 DB14 as a non-azobenzene dye was revealed to be available for the water permeation

309 even when the dye was modified to PTFE membrane. The irradiated visible light

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310 absorbed by DB14 on the membrane is converted to heat in the same manner as

311 rhodamine B. This heat warms the water at the interface of the membrane to form water

312
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vapor that permeates the hydrophobic membrane. The water remained on the membrane
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313 and the permeated and evaporated water had no color in both cases above. Neither
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314 dissolution of DR1 and DB14 into water on the membrane nor the permeation through

315 the membrane occurred. The volumes of the penetrated water through these modified
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316 membranes were comparable to the maximum volume of the permeated water in the
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317 case of rhodamine B solution (approximately 24 µL for 1 h irradiation) even for half

318 time irradiation (0.5 h). Thus, the direct modification of dyes onto the membrane was
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319 ascertained to be beneficial. Next, the double dye modified PTFE membrane was used

320 for the water permeation. The volume of the permeated water recovered under the
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321 membrane increased to 32 µL. It is thought that this membrane could absorb the

322 irradiated visible light (from 385 to 740 nm in wavelength) more effectively than other

323 membranes, enhancing the ability of the water permeation. Thermography images of the

324 double dye modified membrane are shown in supplementary data. From the images, the

325 membrane became hot peculiarly under the light irradiation. When the light was shaded,

326 the membrane got cold quickly, while the water on the membrane was still warm.

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327 (Table 1)

328 For revealing the effects of wavelength band, the region of wavelength of the

329 irradiated light was controlled using a short pass or a long pass filter. When short-

330 wavelength visible light (385~550 nm) that is suitable for the absorption of DR1 was

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331 irradiated to these membranes, the volume of the permeated water through the DB14

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332 modified membrane (8 µL) was lower than that through the DR1 modified one (11 µL).

333 The double dye modified membrane (14 µL) was the best even under this irradiation.

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334 The irradiation of long-wavelength visible light (550~740 nm) resulted in the higher

335 permeation in the DB14 modified membrane (16 µL) than in the DR1 modified one (7

336
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µL). This long-wavelength visible light is suitable for the harvest of DB14. The water
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337 permeation using the double dye modified membrane (14 µL) was comparable to that
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338 with the DB14 modified one. On the other hand, the irradiation of NIR light ranging

339 from 750 to 1050 nm in wavelength also indicated the clear effect of wavelength band
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340 of the irradiated light. While the DR1 modified membrane had a poor activity for the
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341 permeation (4 µL), the DB14 modified and the double dye modified membranes showed

342 14 and 19 µL of the water penetration, respectively. These two membranes are likely to
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343 harvest NIR light effectively as well as visible light. Thus, the adaptation of light

344 harvesting ability of the membrane toward the irradiated light is an important factor to
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345 enhance the performance of the membrane.

346

347 3.4. Water permeation and desalination with dye modified PTFE membranes using

348 simulated sunlight

349 The irradiated light employed above was controlled to be approximately from

350 375 to 740 nm in wavelength. The intensity of the light is nearly equal in the region (see

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351 the web site of Asahi Spectra; http://www.asahi-spectra.com/), which are considerably

352 different from natural sunlight (see Fig. 7). Then, a simulated sunlight from a solar

353 simulator was used for the irradiated light, because the direct application of natural

354 sunlight to seawater desalination shown in Fig. 2 is a goal of this research. Table 2

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355 shows the results of the permeation of distilled water under the light irradiated from a

solar simulator at 1000 W/m2 (1 SUN). Non modified PTFE membrane was inactive in

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356

357 this irradiation. When the DR1 modified and DB14 modified membranes were used, the

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358 volumes of the permeated water were nearly equal (25 µL), which were the similar level

359 to the cases of the visible light irradiation (375~740 nm). In natural sunlight, visible

360
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light with a wavelength of approximately 500 nm has the highest intensity as shown in
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361 Fig. 7. As this light of wavelength 500 nm is suitable for DR1 harvesting, the DR1
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362 modified membrane had the equal activity to the DB14 modified one. On the other hand,

363 the water permeation using the double dye modified membrane was very high (47 µL),
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364 which was approximately 1.5 times to the case of the visible light irradiation (32 µL in
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365 Table 1). As expected above from the good correspondence of the spectrum of this

366 membrane with that of sunlight illustrated in Fig. 7, this membrane harvested sunlight
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367 more efficiently by the cooperation of DR1 and DB14, where the most intense sunlight

368 of wavelength 500 nm was absorbed by DR1 and long-wavelength visible light was
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369 harvested by DB14. In this case, 3 µL of the evaporated water was obtained on the

370 undersurface of the watch glass above the membrane, and totally 50 µL of purified

371 water was produced. As the volume of the recovered water from the membrane was

372 0.43 mL (although this volume is not so accurate), 70 µL of water was vanished from

373 the membrane and about 20 µL of water was not retrieved. This unrecovered water must

374 be moisture vapor in atmosphere and the water spread on the membrane. The effectual

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375 recovery of the purified water must be improved for the practical application of this

376 process.

377 (Table 2)

378 Seawater desalination was finally examined using these dye modified PTFE

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379 membranes by sunlight. An artificial seawater obtained with MARINE ART SF-1

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380 (Fushimi et al., 2016) was employed for the desalination experiment. The membranes

381 modified with DR1 or DB14 were active for the light induced desalination, and the

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382 permeated water was sufficiently desalinated. The electric conductivities of these water

383 were 43 and 34 µS/cm, respectively, whose salinities were estimated to be less than

384
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0.01%. When the double dye modified PTFE membrane was utilized, the permeated
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385 water increased to 44 µL and its low electric conductivity (30 µS/cm) showed the
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386 successful desalination. Water with the electric conductivity lower than 200 µS/cm is

387 evaluated as purified water with salinity less than 0.01%. Thus, the DR1 and DB14
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388 double modified PTFE membrane was the most efficient for the seawater desalination
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389 using a simulated sunlight. The repeatability of this sunlight induced seawater

390 desalination using the double dye modified membrane was tested as listed in Table 3.
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391 The artificial seawater on the membrane was simply replaced prior to the next

392 experiment and no washing of the membrane was carried out for estimating the
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393 degradation of the membrane. The 8 times repeated experiments gave approximately the

394 same results, where the volumes of the permeated water were in the range of from 39 to

395 56 µL. The electric conductivities of all the permeated water corresponded to purified

396 fresh water. Thus, no clear deterioration of the membrane was observed in the repeated

397 test. Fig. 6D illustrates the image of the double dye modified membrane after used for

398 the water permeation experiment more than 20 times. Although the membrane slightly

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399 lost color and became flabby, it preserved the ability of the permeation and desalination

400 even after the use. In conclusion, the membrane modified with both DR1 and DB14 was

401 the most active membrane for the direct solar desalination.

402 (Table 3)

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403

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404 3.5. Energy estimation of the light induced desalination using dye modified PTFE

405 membrane

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406 The efficiency of solar energy conversion was roughly calculated. The contact

407 area of the water droplet (0.5 mL) with the modified PTFE membrane was

408
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approximately 1.13 cm2 (nearly a circle of diameter 1.2 cm). As the simulated sunlight
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409 was irradiated at 1 SUN intensity (1 SUN = 1000 W/m2), the whole energy for this
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410 irradiation area is estimated to about 203 J from the irradiation time (0.5 h) and the

411 contact area (1.13 cm2) of water. The total volume of the permeated and evaporated
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412 water recovered under and above the membrane was 50 µL in the case of the double dye
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413 modified membrane using distilled water. The energy for the vaporization of this

414 volume of water is about 123 J using the heat of evaporation at 20°C (2461 J/g).
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415 Therefore, approximately 60% of the irradiated sunlight energy was used for the

416 production of the purified fresh water. Using the lost volume of water from the
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417 membrane (70 µL from the remained volume 0.43 mL), the efficiency of sunlight

418 became more than 80%. One of the practical indirect solar desalination processes is the

419 system connecting solar water heating with membrane distillation for desalination (Ali

420 et al., 2011). The usual energy efficiency of solar thermal conversion in solar water

421 heating is about 50~70% (Sadhishkumar et al., 2014). As the warmed water in solar

422 water heating has to be transported to membrane desalination apparatus in this indirect

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423 system, energy loss by cooling during the transportation is assumed to be inevitable.

424 Therefore, our direct desalination using the dye modified membrane is superior in terms

425 of not only simplicity of the system but also efficient utilization of sunlight.

426 The energy efficiency of purified water production of our process was estimated

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427 to about 1129 kWh/m3-water. This efficiency is considerably lower than reverse

osmosis (2-6 kWh/m3-water) and common membrane distillation (40-45 kWh/m3-water)

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428

429 (Tong et al, 2016). These existing processes generally require the energy of fossil fuel

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430 for pressuring or heating water, respectively, whereas our process is essentially free

431 from fossil fuel to emit no CO2. On the other hand, our process is equivalent to the

432
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membrane distillation by the direct joule heating using carbon nanotube (1250 kWh/m3-
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433 water) in energy efficiency (Dudchenko et al., 2017). It is thought that our desalination
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434 process using sunlight is a talented one having a high potential for sustainable fresh

435 water production. These energy estimations are simply the results of a small scale
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436 experiment, and we are now attempting scaling-up and enhancing the efficiency of our
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437 process.

438
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439 4. CONCLUSIONS

440 This paper reports the light induced water permeation using PTFE membranes
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441 modified with dyes as light harvesting component. In our previous paper (Fujiwara,

442 2017), the DR1 modified PTFE membrane is applied, where the repetitive photo

443 isomerization caused by the irradiation of visible light evaporates water on the

444 membrane. This paper revealed that the aqueous solution of rhodamine B permeated

445 non modified PTFE membrane to be purified under visible light irradiation. This result

446 indicated that non-azobenzene dye and its aqueous solution are available in the light

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447 induced water permeation and purification. At the same time, the direct modification of

448 dye to the membrane is suggested to be more preferable. The PTFE membrane modified

449 with DB14 that is another non-azobenzene dye was also active for the water permeation.

450 Visible light irradiated to these non-azobenzene dyes was release as heat that vaporized

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451 the water on the membrane. The water vapor thus formed permeated the PTFE

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452 membrane to be recovered under the membrane as purified water. From these results, a

453 PTFE membrane modified with both DR1 and DB14 was employed for the water

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454 permeation. This membrane absorbed almost whole visible light and the volume of the

455 permeated water was higher than the membranes modified with DR1 or DB14. This

456
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membrane was more effective when a simulated sunlight was used. When an artificial
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457 seawater was applied, the permeated water was sufficiently desalinated to become fresh
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458 water. These results ascertained that the desalination process using solar light directly is

459 well realizable by the PTFE membrane modified with both DR1 and DB14. This
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460 process is expected to produce purified water without the consumption of fossil fuels. A
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461 major challenge of the membrane desalination processes using solar energy including

462 our process is the low energy density of sunlight, which naturally requires huge
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463 membrane area. The practical plants of these processes will be operated on desert areas

464 or at sea in order to address the low energy density. The combination with light
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465 concentrating installation is thought to be effective for reducing the area of the

466 membrane. In addition, as the particles and natural organic matters in seawater shade

467 sunlight to reduce the performance of the membrane, they should be effectually

468 eliminated in the practical processes.

469

470 Acknowledgement

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471 This work was supported by a Grant-in-Aid for Scientific Research (Grant

472 Number: JP16H03002) from the Japan Society for the Promotion of Science (JSPS).

473 Authors thank Dr. Yoshio Masuda (AIST) for his collaboration in energy estimation.

474 Authors also thank Prof. Shingo Matsukawa (Tokyo University of Marine Science and

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475 Technology) and Dr. Mitsuhiro Kanakubo (AIST) for their helps.

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476

477 References

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481 Change 9, S31–S49.
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485 Ding, Z., Liu, L., El-Bourawi, M.S., Ma, R., 2005. Analysis of a solar-powered

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487 Dongare, P.D., Alabastri, A., Pedersen, S., Zodrow, K.R., Hogan, N.J., Neumann, O.,

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494 El-Bialy, E., Shalaby, S.M., Kabeel, A.E., Fathy, A.M., 2016. Cost analysis for

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507 liquefaction processes. Energy Fuels 30, 7916−7922.

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508 Ghasemi, H., Ni, G., Marconnet, A.M., Loomis, J., Yerci, S., Miljkovic, N., Chen, G.,

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516 Ito, Y., Tanabe, Y., Han, J., Fujita, T., Tanigaki K., Chen, M., 2015. Multifunctional

517 porous graphene for high-efficiency steam generation by heat localization. Adv. Mater.

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520 consumption analysis and water production costs (a review). Desalination 308, 89–101.

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521 Koschikowski, J., Wieghaus, M., Rommel, M., 2003. Solar thermal-driven

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523 Li, C., Goswami, Y., Stefanakos, E., 2013. Solar assisted sea water desalination: a

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526 B.J., 2004. Comparative study on the effect of RF and DBD plasma treatment on PTFE
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529 T., 2016. Bioinspired bifunctional membrane for efficient clean water generation. ACS
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530 Appl. Mater. Interfaces 8, 772–779.

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532 recycling by air gap membrane distillation. Desalination 187, 291–301.

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534 Sustainable Built Environ. 3, 153–165.

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540 Shatat, M., Worall, M., Riffat, S., 2013. Opportunities for solar water desalination

541 worldwide: review. Sustainable Cities Soc. 9 67–80.

542 Tong, T., Elimelech, M., 2016. The global rise of zero liquid discharge for wastewater

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544 6846−6855.

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545 Youxian, D., Griesser, H.J., Mau, A.W.-H., Schmidt, R., 1991. Surface modification

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547 Yu, S., Zhang, Y., Duan, H., Liu, Y., Quan, X., Tao, P., Shang, W., Wu, J., Song, C.,

548 Deng, T., 2015. The impact of surface chemistry on the performance of localized solar-

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550 Zhang, L., Tang, B., Wu, J., Li, R., Wang, P., 2015. Hydrophobic light-to-heat
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551 conversion membranes with self-healing ability for interfacial solar heating. Adv. Mater.

552 27, 4889–4894.

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553
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554 Legends of Figures

555

556 Fig. 1. (A) Common air-gap membrane distillation with solar water heating, (B) solar

557 desalination using dye modified PTFE membrane.

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558 Fig. 2. A proposed process of solar desalination of seawater using dye modified PTFE

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559 membrane.

560 Fig. 3. Molecular structures of (A) disperse red 1 (DR1), (B) disperse blue 14 (DB14),

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561 and (C) rhodamine B.

562 Fig. 4. Absorption spectra of aqueous solution of rhodamine B, and the ethanol

563 solutions of DR1 and DB14.

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564 Fig. 5. The plots of the volumes of the permeated and evaporated water, and the
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565 temperature of the remained water on the membrane after 1 h irradiation of visible light

566 as a function of the concentration of rhodamine B.

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567 Fig. 6. Images of (A) DR1 modified PTFE membrane, (B) DB14 modified PTFE
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568 membrane, (C) double dye (DR1 and DB14) modified PTFE membrane and (D) double

569 dye modified PTFE membrane after using for more than 20 times experiment.
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570 Fig. 7. Diffuse reflectance UV-vis-NIR spectra of dyes modified membranes. The value

571 of the Y-axis of DR1 modified membrane is reduced to half and that of DB14 modified
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572 one is doubled for fitting the level. The solar irradiance spectrum is also overlaid.

573

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1 Table 1

2 Distillated water permeation through dye modified PTFE membranes under light

3 irradiation.a

Membrane Irradiated lightb Vol. of remain Vol. of permeated

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water (mL) water (×10-3 mL)c

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DR1 modified 385~740 0.45 23 (8)

DB14 modified 385~740 0.44 28 (8)

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DR1+DB14 modified 385~740 0.44 32 (9)

DR1 modified 385~550 0.47 11 (3)

DB14 modified 385~550

U 0.48 8 (2)
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DR1+DB14 modified 385~550 0.47 14 (3)
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DR1 modified 550~740 0.45 7 (2)

DB14 modified 550~740 0.45 16 (2)

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DR1+DB14 modified 550~740 0.46 14 (3)

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DR1 modified 750~1050 0.47 4 (~0)

DB14 modified 750~1050 0.46 14 (~0)

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DR1+DB14 modified 750~1050 0.45 19 (2)

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a
4 0.50 mL of distillated water was put on membrane. Irradiation time was 0.5 h.
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b
5 Visible light 385~740 nm was irradiated without optical filter using VIS mirror

6 module. Visible light 385~550 nm and 550~740 nm were irradiated with a short pass

7 filter (SVX550) or a long pass filter (LVX550), respectively, using VIS mirror module.

8 NIR light 750~1050 nm was irradiated without optical filter using NIR mirror module.
c
9 In parentheses, the volumes of water recovered on the undersurface of the watch glass

10 above the membrane.

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1 Table 2

2 Water permeation through dye modified PTFE membranes under simulated sunlight

3 irradiation.a

Membrane Water Vol. of Vol. of Electric

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remain permeated conduct.

water (×10-3 (µS/cm)

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water (mL)

mL) b

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Non modified Distilled water 0.50 0 (0) –

DR1 modified Distilled water 0.44 25 (2) –

DB14 modified
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Distilled water 0.45 25 (8) –
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DR1+DB14 modified Distilled water 0.43 47 (3) –
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DR1 modified Artificial seawater 0.44 30 (2) 43

DB14 modified Artificial seawater 0.45 31 (2) 34

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DR1+DB14 modified Artificial seawater 0.37 44 (3) 30

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a
4 0.50 mL of water was put on membrane. Irradiation of simulated sunlight from solar

5 simulator (XEF-300, SAN-EI ELECTRIC) for 0.5 h at 1 SUN.

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b
6 In parentheses, the volumes of water recovered on the undersurface of the watch glass
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7 above the membrane.

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1 Table 3

2 Repeated artificial seawater desalination using double dye (DR1 and DB14) modified

3 PTFE membrane under simulated sunlight.a

Number of Vol. of remain water Vol. of permeated Electric conductivity

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times (mL) water (×10-3 mL)b (µS/cm)

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1 0.40 44 (1) 36

2 0.41 39 (2) 61

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3 0.41 56 (1) 137

4 0.41 50 (3) 42

5 0.42
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50 (3) 21
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6 0.41 50 (3) 18
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7 0.41 52 (5) 20

8 0.41 52 (4) 47
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a
4 0.50 mL of water was put on membrane. Irradiation of simulated sunlight from solar
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5 simulator (XEF-300, SAN-EI ELECTRIC) for 0.5 h at 1 SUN.

b
6 In parentheses, the volumes of water recovered on the undersurface of the watch glass
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7 above the membrane.

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8
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1 Figure 1

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5 (A) (B)

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Solar Light Solar Light
Solar Water
Heating

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Cold Water
Warmer Water
Warmer Water

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Hydrophobic Membrane Hydrophobic Membrane
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Dye

Condensed Water Condensed Water

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6
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8
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9 Fig. 1. (A) Common air-gap membrane distillation with solar water heating, (B) solar
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10 desalination using dye modified PTFE membrane.

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1 Figure 2

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Sunlight

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Dye Modified
Membrane
Seawater

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Desalinated Water
(Purified Fresh Water )
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6
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8 Fig. 2. A proposed process of solar desalination of seawater using dye modified PTFE

9 membrane.

10

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1 Figure 3

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5 (A) (B) (C)

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6

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7
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8

9 Fig. 3. Molecular structures of (A) disperse red 1 (DR1), (B) disperse blue 14 (DB14),
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10 and (C) rhodamine B.

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1 Figure 4

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DR1 Rhodamine B
Absorption (au)

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DB14

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400 500 600 700 800

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5
Wavelength (nm)
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8 Fig. 4. Absorption spectra of aqueous solution of rhodamine B, and the ethanol

9 solutions of DR1 and DB14.

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1 Figure 5

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30

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Temperature of remained water (°C)
Volume of permeated water (µL)

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20

15

10
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Permeated water
5
Evaporated water
Temperature
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0
0.0 0.5 1.0 5 10 15 20

Concentration of rhodamine B (mM)

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5
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7
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8 Fig. 5. The plots of the volumes of the permeated and evaporated water, and the

9 temperature of the remained water on the membrane after 1 h irradiation of visible light
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10 as a function of the concentration of rhodamine B.

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1 Figure 6

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5 (A) (B) (C)

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6
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7 (D)
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10
C

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12 Fig. 6. Images of (A) DR1 modified PTFE membrane, (B) DB14 modified PTFE

13 membrane, (C) double dye (DR1 and DB14) modified PTFE membrane and (D) double

14 dye modified PTFE membrane after using for more than 20 times experiment.

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1 Figure 7

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DR1 modified DR1+DB14 modified
Solar-Irradiance (W/m3/nm)

Solar light

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DB14 modified
Kubelka-Munk

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300 400 500 600 700 800 900 1000

Wavelength (nm)
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5
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7
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8 Fig. 7. Diffuse reflectance UV-vis-NIR spectra of dyes modified membranes. The value

9 of the Y-axis of DR1 modified membrane is reduced to half and that of DB14 modified
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10 one is doubled for fitting the level. The solar irradiance spectrum is also overlaid.
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Highlights

Solar desalination of seawater using double-dye-modified PTFE

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membrane

Masahiro Fujiwara and Masaki Kikuchi

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Aqueous solution of rhodamine B permeated through PTFE membrane by
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visible light irradiation.
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Permeated water through PTFE membrane contained no rhodamine B to be

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purified.
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DB14 as a non-azobenzene dye was effective for the water permeation by

visible light irradiation.

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PTFE membrane modified with DR1 and DB14 was very active for

seawater desalination with sunlight.