Superhydrophobic sodium alginate/cellulose

aerogel for the dye adsorption and oil-water

separation
Huimin Li
Jiangnan University
Jingyi Huang
Jiangnan University
Chaoran Meng
Jiangnan University
Shen Shen
Jiangnan University
Hongbo Wang
Jiangnan University
Jiajia Fu (  kathyfjj@126.com )
Jiangnan University

Research Article

Keywords: Polysaccharide-based aerogel, Hydrophobicity, Dye adsorption, Oil-water separation

Posted Date: October 13th, 2022

DOI: https://doi.org/10.21203/rs.3.rs-2134219/v1

License:   This work is licensed under a Creative Commons Attribution 4.0 International License.
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 1 Superhydrophobic sodium alginate/cellulose aerogel for the dye

2 adsorption and oil-water separation

3 Huimin Li a,b, Jingyi Huang a, Chaoran Meng a, Shen Shen a,b, Hongbo Wang a, Jiajia Fu a,b

a
4 Jiangsu Engineering Technology Research Centre for Functional Textiles, Jiangnan University,

5 No.1800 Lihu Avenue, Wuxi, P.R. China

b
6 China National Textile and Apparel Council Key Laboratory of Natural Dyes, Soochow University,

7 Suzhou 215123, China

8 Abstract

9 The wide application of polysaccharide-based aerogel is limited by its hydrophilicity. To solve this

10 problem, sodium alginate/ sodium carboxymethyl cellulose (SA/CMC) with silica nanoparticles and

11 methyl trimethoxysilane as hydrophobic modifiers was prepared in this study. The sodium alginate (SA)

12 and sodium carboxymethyl cellulose (CMC) were selected because of their low cost and easy of

13 combination with the other two materials. After the silane reagent modification, Ca2+ crosslinking,

14 surface plasma treatment, thermochemical vapor deposition and freeze-drying methods, the aerogel get

15 density of 0.080 g/cm3, high porosity of 94%, three-dimensional porous structure with great

16 adsorbed ability. This superhydrophobic SA/CMC aerogel exhibits excellent water stability, appropriate

17 compressive strength and good adsorption capacity of cationic dye methylene blue (MB). And the

18 adsorption process is analyzed by adsorption kinetics. Meanwhile, this aerogel gets great absorbency and

19 efficiency towards varieties of organic solvents, which gives it great potential of being used in the field

20 of oil-water separation, textile dye wastewater treatment, etc. Moreover, this aerogel is expected to be


Corresponding author; e-mail: kathyfjj@126.com ; wxwanghb@163.com
21 recycled after washing.

22 Keywords

23 Polysaccharide-based aerogel; Hydrophobicity; Dye adsorption; Oil-water separation;

24 Introduction

25 With the development of the industrialization, organic water pollution (e.g., textile dye wastewater

26 treatment, oil spill, etc) is becoming more and more serious, which caused serious problem to the

27 ecological environment (Lee et al. 2017). Thus, developing novel materials for removing the organic

28 pollutants out of water effectively is of great urgent. And aerogels showed great potential under this

29 circumstances (Zhang et al. 2020). Aerogel is a sort of porous and light-weight materials widely used in

30 the field of catalysis (Niu et al. 2020), adsorption and environmental clean-up (Zhang et al. 2017, Matias

31 et al. 2015, Perdigoto et al. 2012, Guan et al. 2020, Adebajo et al. 2003), acoustic transducers (Long et

32 al. 2021), energy storage devices (Long et al. 2008), thermal isolation (Zheng et al. 2020), flame retardant

33 (Chen et al. 2016), chemical sensors (Plata et al. 2004), and biomedical and pharmaceutical applications

34 (Smirnova et al. 2004, Ulker & Erkey 2014, Yan et al. 2020). Up to our knowledge, the potential

35 application of the aerogel is strongly relied on the materials and microstructure. The microstructure can

36 be controlled during the preparation process, including the sol-gel transition (gelation), network

37 perfection (aging) and gel-aerogel transition (drying) (Zuo et al. 2015). The starting precursors, operating

38 and provision requirements are the decisive factor in a sol-gel reaction of wet chemical synthesis

39 approach to prepare aerogels. Moreover, the generation of the 3D porous network is the most determinant

40 aspect of aerogel fabrication (Maleki 2016, Estella et al. 2007). Although the biodegradable

41 polysaccharide-based aerogels showed great promise in the area of oil-water separation, they are

42 extremely fragile and easy to collapse in water due to the hydrophilicity property of the materials (Fu &
43 Guo 2022, Alvarez-Lorenzo et al. 2013, Reches & Gazit 2003, Autissier et al. 2010, Benbettaieb et al.

44 2016). Therefore, the polysaccharide aerogel without hydrophobic modification, as adsorbent or catalyst,

45 will seriously affect the adsorption effect or catalytic efficiency. It has practical significance to extend

46 and promote the application of the eco-friendly polysaccharide aerogel by changing its hydrophilicity.

47 Alginate and cellulose, both natural polysaccharide that have shown great potential as the most

48 important biocompatible and eco-friendly polymers in nature, which are rich in resources. The

49 evaporation of absorbed water molecules often causes the structure of aerogel to collapse. There are

50 limited its application due to poor mechanical properties and excellent hydrophilicity in the dye

51 adsorption, oil-water separation and recyclability. On the one hand, sodium alginate (SA) can form a 3D

52 network with a unique “egg-box” structure upon ionic crosslinking with divalent cations such as calcium,

53 because the cations cause the G-units on neighboring polysaccharide chains to interact, corresponding to

54 the gels stack that form the structure of the cross-linking network (Jing et al. 2022, Gao et al. 2021, Jeong

55 et al. 2010). Meantime, cellulose derivative aerogels can be prepared by derivatization of cellulose and

56 chemical crosslinking of crosslinking agent (Tan et al. 2001). Sodium carboxymethyl cellulose (CMC),

57 as a solubility polysaccharide with biocompatibility and biodegradation, is a common derivates formed

58 by the carboxymethylation of the hydroxyl group of cellulose (Lin et al. 2016). CMC can facilely and

59 quickly cross linked with metal ions (such as Ca2+, Mg2+, Al3+ and Fe3+) in non-toxic and eco-friendly

60 reaction environment (Lin et al. 2016, Nie et al. 2004, Li et al. 2013, Nadagouda & Varma 2007). On the

61 other hand, the bionic superhydrophobic materials, as a recent research hotspot, are mainly constructed

62 according to the superhydrophobic lotus surface and typical “rose petal” effect in nature (Li et al. 2017).

63 The constructed fabric surfaces with microtemplates for patterning, which are based on the morphology

64 of particles coated on the textile fibre and exhibit an anti-wetting property. Moreover, the
65 superhydrophobic surfaces generally needs the introduction of surface roughness. The hydrophobic

66 interface with hierarchical cellular structure can be achieved by constructing rough micro and nano

67 texturing or introducing low surface energy substances (Li et al. 2017, Wang & Jiang 2007). Hereby, the

68 efficient way of superhydrophobic polysaccharide-based aerogel via silane reagent modification is the

69 most common preparation (Feng et al. 2015). Besides, plasma processing is a kind of modification

70 method with fast etching speed, high uniformity and low pollution in the processing method of

71 microscopic rough structure (Tsougeni et al. 2007). Moreover, the vapour deposition of hydrophobic

72 silanes on sponge-like ultra-porous nanocellulose aerogels can separate the mixed oil and water liquids

73 (Cervin et al. 2012). Xiao et al. developed a superhydrophobic and superelastic graphene oxide/nanofiber

74 aerogel (GNA) after chemical modification and crosslinking via vapor deposition of

75 hexadecyltrimethoxysilane to quickly separate oil-in-water emulsions with an extremely high flux (Xiao

76 et al. 2018). Yang et al. fabricated a robust and superhydrophobic sodium alginate/graphene oxide/silicon

77 oxide aerogel (SA/GO/SiO2-M) by calcium ion cross-linking self-assembly and chemical vapor

78 deposition, which possesses high efficiency in the separation of surfactant-stabilized water-in-oil

79 emulsions with excellent reusability (Yang et al. 2021).

80 Herein, a superhydrophobic SA/CMC aerogel with silica nanoparticles was fabricated via silane

81 reagent modification, Ca2+ crosslinking, surface plasma treatment, thermochemical vapor deposition and

82 freeze-drying methods. The aerogel is explored the adsorption performance and oil-water separation

83 performance for cationic dye methylene blue (MB) and organic solvents. The effect of multi-step process

84 on hydrophobicity was studied in detail through the characterization of selective wettability,

85 adsorbability of various organic solvents, and oil-water separation capability. Meanwhile, the adsorption

86 process of cationic dye MB on the superhydrophobic SA/CMC aerogel was analyzed by the adsorption
 87 kinetics analysis. This study shows that the superhydrophobic SA/CMC aerogel are a promising material

88 in treating wastewater pollution from different fields.

89 2. Materials and methods

90 2.1 Materials

91 Sodium carboxymethyl cellulose (CMC, viscosity: 20 g/L solution, 300−800 mPa・s) and sodium

92 alginate (SA, viscosity: 10 g/L solution, 20℃, ≥ 0.02 Pa・s) were obtained from Sinopharm Chemical

93 Reagent Co., Ltd. (China). Silica (SiO2) nanoparticles with diameter 15 ± 5 nm and the purity of 99.8

94 wt% was supplied by Shanghai Macklin Biochemical Co., Ltd. (China). Trimethoxymethylsilane

95 (MTMS, purity ≥ 98 wt%), calcium chloride anhydrous (CaCl2), hexane, anhydrous ethanol (AE) and

96 other chemical reagents were also purchased from Sinopharm Chemical Reagent Co., Ltd. (China).

97 Deionized water (DW) used in the experiments was obtained using an ULUPURE pure water/water

98 system.

99 2.2 Preparation of the superhydrophobic SA/CMC aerogel

100 In our present study, we prepared the superhydrophobic SA/CMC aerogel via silane reagent

101 modification, Ca2+ crosslinking, surface plasma treatment, thermochemical vapor deposition and freeze-

102 drying methods. SA and CMC were dissolved into 2.0 wt % with optimal stock solutions volume ratios

103 of SA/CMC (m/m) of 1/1 proceeding 2 h at 850 rpm under the condition of agitation at 30 ℃. By the

104 way, the freeze-dried sample obtained at this time was distinguished as the SA/CMC aerogel. Briefly, a

105 certain amount of silica nanoparticles (m(SA): m(CMC): m(SiO2) =10:10:1) was added to the mixture

106 and stirred at 850 rpm for 1 h, and 10 % of the volume fraction of MTMS was also added into the mixture

107 and stirred at 850 rpm for 1 h. Then, the evenly dispersed mixture was sonicated for 30 min before

108 freezing at -80 ℃ to remove large trapped air bubbles. After freeze-drying, the resulting aerogel was
109 immersed into impregnation solution (m (CaCl2): m (AE): m (DW) = 2:80:20) for 12 h, and washed with

110 an excess amount of DW and freeze-dried again. The obtained aerogel was surface modified by low-

111 temperature plasma treatment in a condition of argon atmosphere for 10 min. Afterward, the aerogel was

112 obtained in the simple reaction device of cup in cup with MTMS at 80 ℃ for 4 h. This device of cup in

113 cup is mainly to prevent direct contact between aerogel sample and MTMS liquid. After fully reaction,

114 the aerogel was placed in a vacuum drying oven with low pressure to remove the unreacted MTMS.

115 Finally, the superhydrophobic SA/CMC aerogel was obtained (Scheme 1, Support Information S1).

116

117 Scheme 1. Schematic illustration the treatment and possible hydrophobic modification mechanism of the

118 superhydrophobic SA/CMC aerogel.

119 2.3 Physicochemical Characterizations of the superhydrophobic SA/CMC aerogel

120 The surface morphologies of samples were captured by scanning electron microscope (SEM

121 SU1510, JPN). The molecular and crystallographic structures of samples were investigated by FT-IR

122 spectrophotometer (Nicoletis10, USA) using KBr disk method in the range of 4,000−500 cm-1. The
123 crystal-lographic structures of samples were characterized by X-ray diffraction diffractometer (XRD D2

124 PHASER, GER) with a CuKa radiation (k = 0.15405 nm) with a scanning rate of 2 min -1 at 40 kV and

125 40 mA. The un-treated linen fabric (s0) was also analyzed for comparison.

126 Measurement for the physical properties of the superhydrophobic SA/CMC aerogel

127 The thermal stabilities of samples were determined by thermo-gravimetric analyzer (TGA, Q500,

128 USA) with a heating rate of 10 ℃ min-1 under N2 environment from 40 C to 800 ℃ as the test

129 temperature range. Stress-strain curves were obtained by Universal Mechanical Materials Tester with

130 loading speed of 10 mm·min-1 and 80 % of strain is the test end point. Each sample was tested three times

131 to get the average value.

132 2.4 Density and porosity

133 The diameter and thickness of samples (circular shape) were measured separately. The density was

134 calculated using the formula (1).

𝑚
135 ρ= (1)
𝑉

136 where m and V are the weight and volume of samples, respectively.

137 The liquid displacement method was used to determine the porosity of samples. The samples (cube,

138 1 cm×1 cm×1 cm) were put into anhydrous ethanol (AE) to reach a saturation point. All tested samples

139 were gently blotted with filter paper to remove the excess AE and to get the immediately weighed (W).

140 The porosity was calculated using the formula (2).

(W−𝑊0 )
141 𝑃 (%) = × 100% (2)
ρ𝑎 V

142 where W0 and W are the weight of samples before and after being immersed in AE, respectively; V is

143 the sample volume before immersion and ρa is the density of alcohol.

144 2.5 Measurement of water stability for the superhydrophobic SA/CMC aerogel
145 The water contact angles (WCAs) were measured at room temperature and ambient relative

146 humidity using a DSA25 contact angle analyzer connected to drop shape analysis software. The water

147 contact angles for each sample were measured more than five times on the SA/CMC aerogel and the

148 superhydrophobic SA/CMC aerogel. The water stability of the prepared aerogel in the water was also

149 investigated (Support Information S2).

150 2.6 Dye adsorption performance test

151 Methylene blue trihydrate (C16H18ClN3S·3H2O) (Kannan & Sundaram 2001) was dissolved in

152 various concentrations (0.6 mg/L 0.8 mg/L 1.0 mg/L 2.0 mg/L 4.0 mg/L), which were used as MB

153 standard solutions of the concentration required by the experiment. DW was used as control group and

154 measurement baseline. Then the standard concentration gradient of MB solution of samples was

155 determined spectrophotometrically at 664 nm following the Bouguer‐Beer‐Lambert Law (Mayerhofer et

156 al. 2020). The concentration of residual dye in different MB solution was measured after equal-weight

157 samples reached the adsorption equilibrium in 50 mL centrifuge tube at 200 rpm. The removal percentage

158 and adsorption value of MB were calculated using the formula (3)(4)(5).

𝐶0 −𝐶𝑒
159 𝑅𝑒 (%) = × 100% (3)
𝐶0

(𝐶0 −𝐶𝑒 )𝑉𝑑 ×𝑁

160 𝑄𝑒 = (4)
𝑚0

(𝐶0 −𝐶𝑡 )𝑉𝑑 ×𝑁

161 𝑄𝑡 = (5)
𝑚0

162 where Re (%), Qe and Qt (mg/g) are dye removal percentage, dye adsorption capacity at equilibrium and

163 t moment, respectively; C0、Ce and Ct (mg/L) are the dye concentration at initial, equilibrium and t

164 moment, respectively; Vd (L) is the volume of the dye solution; mf (g) is the initial mass of the aerogel;

165 N is dilution ratio.

166 2.7 The adsorption kinetics of the superhydrophobic SA/CMC aerogel

167 The pseudo-second-order model and intra-particle diffusion can be used to explore the adsorption

168 rate and behavior of pollutants on aerogel for studying its adsorption kinetics (Vimonses et al. 2009, Ho

169 & McKay 1999). The pseudo-second-order model can be used to judge the adsorption properties of

170 aerogel, which were calculated using the formula (6).

𝑡 1 𝑡
171 = + (6)
𝑄𝑡 𝐾2 𝑄𝑒 2 𝑄𝑒

172 Where Qe, Qt (mg·g-1) are the adsorption capacity at equilibrium and t moment, respectively. K2 (mg·g-

173 1
·min-1) is the pseudo-second-order model rate constant and t (min) is adsorption time.

174 The adsorption rate of adsorbents on porous material is usually controlled by the transfer rate at the

175 solid-liquid interface or inside the particle. The intra-particle diffusion within the particle is often used

176 to evaluate the diffusion mechanism of the adsorption process, which were calculated using the formula

177 (7).

1⁄
178 𝑄𝑡 = 𝐾𝑖𝑑 𝑡 2 + 𝐶𝑖𝑑 (7)

179 Where Kid (mg·g-1·min-1/2) is diffusion rate constant of the intra-particle diffusion. The larger the

180 diffusion rate constant is, the easier the adsorbent diffuses inside the adsorbent. Cid is a constant involving

181 the boundary molecular layer including thickness and boundary layer. A linear line with slope Kid and

182 intercept Cid can be obtained by drawing t1/2 and Qt. The adsorption process is controlled by a single rate

183 of intra-particle diffusion if the line passes through the origin. Otherwise, the adsorption process is

184 controlled by both intra-particle and interfacial diffusion (Kannan & Sundaram 2001).

185 2.8 Adsorption performance test of simulated organic pollutants

186 In order to test the adsorption performance of the superhydrophobic SA/CMC aerogel on organic

187 pollutants, such as hexane, chloroform, oil pumping, AE, toluene and paraffin liquid were selected as the

188 adsorbent of organic solvents. And the adsorption capacity and adsorption rate of prepared aerogel were
189 measured respectively to evaluate the adsorption performance of the prepared aerogel. Samples of the

190 same weight were put into 35 mL of various organic solvents to reach adsorption equilibrium at room

191 temperature, then removed from various organic solvents. All tested samples needed gently blotted with

192 filter paper to remove the excess various organic solvents and got the immediately weighed. Each sample

193 was tested three times to get the average value. The adsorption performance was calculated using the

194 formula (8)(9).

𝑚𝑠 −𝑚0
195 𝑀𝑜𝑖𝑙⁄ = (8)
𝑜𝑟𝑔 𝑚0

ρ 𝑚𝑠 −𝑚0
196 𝑉𝑜𝑖𝑙⁄ = × (9)
𝑜𝑟𝑔 ρ𝑜𝑖𝑙 𝑚0
⁄𝑜𝑟𝑔

197 where Moil/org (g/g) is mass adsorption capacity ratio; Voil/org (cm3/cm3) is the volume adsorption capacity

198 ratio; ms and m0 (g) are the weight of samples before and after being immersed in various organic solvents;

199 ρ and ρoil/org (g/cm3) are the density of aerogel and various organic solvents, respectively.

200 2.9 Oil-water separation experiment

201 Hexane and chloroform were selected as two kinds of oils and organic solvents with opposite density

202 compared with water. Chloroform (ρchloroform > ρwater) and hexane (ρhexane < ρwater) were dyed red with sudan

203 red G and DW blue with methylene blue. The oil-water separation performance of the superhydrophobic

204 SA/CMC aerogel (circular shape, diameter: 15 mm ± 0.1mm, thickness: 3 mm ± 0.1mm) was

205 quantitatively characterized by filtration with 10 mL syringe. Chloroform, hexane and DW were mixed

206 at a 1:1 volume ratio to form 4 mL oil-water mixture, which poured into the 10 mL syringe

207 containing aerogel. Meanwhile, the glass bottle was placed under the syringe hole as a liquid collection

208 device to conduct oil-water separation test and observe the effect. The separation efficiency is

209 characterized by the volume ratio or mass ratio of the liquid collected before and after separation. The

210 separation efficiency is calculated by measuring the mass of the liquid before and after separation using
211 the formula (10):

mb
212 η(%) = × 100% (10)
ma

213 where η (%) is the separation efficiency; ma and mb (g) are the mass of oil before and after filtration,

214 respectively.

215 The oil-water separation flow rate of aerogel can be expressed by the fluid flux of aerogel (F), which

216 is an important index to measure the oil-water separation performance of aerogel and can be obtained by

217 the following formula (11):

218 F=
V
A
× 𝑡 (11)

219 Where F is the fluid flux of aerogel; V (mm 3) is the volume of filtrate collected after separation

220 experiment through aerogel; A (mm2) is the effective filtration area of separation experiment;  t (s) is

221 the time required for the whole oil-water separation experiment to pass through the aerogel.

222 3 Results and Discussion

223 3.1. Characterization of the superhydrophobic SA/CMC aerogel

224 The morphology is a vital feature for various samples. Fig.1 shows the microstructure of the

225 SA/CMC aerogel and the superhydrophobic SA/CMC aerogel. The surface of the SA/CMC aerogel is

226 smooth and flat, and the pore structure is not obvious and irregular with small cracks locally. After

227 hydrophobic modification, the morphological changes of the superhydrophobic SA/CMC aerogel are

228 obviously observed. The porous structure presents an increasingly pronounced pore in size of 20 μm with

229 rough surface.

230

231 Fig. 1. Scanning electron microscope (SEM) images of (a, b) the SA/CMC aerogel and its high

232 magnification, (c, d) the superhydrophobic SA/CMC aerogel and its high magnification.

233

234 The FIIR spectra of the SA/CMC aerogel and the superhydrophobic SA/CMC aerogel are compared

235 in Fig. 2. The bands of SA at 1600 cm-1 are attributed to asymmetric stretching vibrations of COO - (Jiao

236 et al. 2016). The absorption peaks at 1600 cm-1 and 2920 cm-1 are found in all spectra, which are mainly

237 ascribed to the carbonyl group (C=O), and the C-H bond on the molecular chain of SA and CMC,

238 respectively. The characteristic peaks at 3350 cm-1 in all spectra are ascribed to O-H on SA and CMC.

239 The superhydrophobic SA/CMC aerogel showed several new absorption peaks at 1269 and 768 cm−1

240 appeared due to Si-O and Si-O-Si bonds in silicane, respectively. The characteristic peaks at 2980 cm-1

241 corresponded to the vibrations of CH3 bond (Robb et al. 2002) (Zhou et al. 2018, Zhou et al. 2015). In

242 addition, C-O stretching vibration absorption peaks at 1100−1000 cm-1 are slightly strengthened, which

243 is probably due to the coincidence of Si-O-Si absorption peaks. These indicate that MTMS successfully

244 modified the superhydrophobic SA/CMC aerogel and formed covalent bond with hydroxyl group

245 through dehydration condensation.

 SA/CMC aerogel

Transmittance (%)
2920
2980
3350 1600
1269
Superhydrophobic SA/CMC aerogel
768

4000 3000 2000 1000

Wavenumbers (cm-1)
246
247 Fig. 2. FT-IR spectra of the SA/CMC aerogel and the superhydrophobic SA/CMC aerogel.

248

249 The crystalline structures of the SA/CMC aerogel and the superhydrophobic SA/CMC aerogel were

250 determined by X-ray diffraction patterns. Obviously, Fig. 3 exhibits the SA/CMC aerogel has the higher

251 crystallinity than the superhydrophobic SA/CMC aerogel. There are two distinct characteristic diffraction

252 peaks at 2θ =10.2° and 2θ =21.5° in the SA/CMC aerogel, while there is not obvious diffraction peak in

253 the superhydrophobic SA/CMC aerogel. The main reason is that the adding of SiO2 nanoparticles and

254 trimethoxymethylsilane and subsequent hydrophobic modification disrupt the arrangement of polymer

255 crystals and form irregular and amorphous regions leading to the low crystallinity of superhydrophobic

256 SA/CMC aerogel (Abhari et al. 2017). It ensured the uniform mixing of them and prevented the

257 crystallization behavior of the SA/CMC aerogel. Thus the amorphous composite superhydrophobic

258 SA/CMC aerogel formed (Chang et al. 2009).

 Intensity(%)
Intensity (%)
20 40 60
2 Theta (°)

SA/CMC aerogel

Superhydrophobic SA/CMC aerogel

20 40 60 80
2 Theta (°)
259
260 Fig. 3. X-ray diffraction pattern of the SA/CMC aerogel and the superhydrophobic SA/CMC aerogel.

261

262 3.2 The thermal stability of the superhydrophobic SA/CMC aerogel

263 The thermo-stabilities of the SA/CMC aerogel and the superhydrophobic SA/CMC aerogel were

264 evaluated by the thermogravimetry analysis (TGA) and differential thermogravimetry (DTG). As shown

265 in Fig. 4, the two kinds of aerogels exhibit four steps of active weight loss with elevating temperature.

266 The rapid weight loss below 100 °C was attributed to the release of moisture from the aerogels. In the

267 dehydration stage, the weight loss rate of the SA/CMC aerogel and the superhydrophobic SA/CMC

268 aerogel reached about 19% and 13 %, respectively. The main reason is that the escape of adsorbed water

269 on the surface and internal pores of aerogels during evaporation. It is speculated that the reason for the

270 difference is that the internal and surface structures of the two kinds of aerogels are significantly different

271 with pore sizes and adsorbed moisture content. On the other hand, the differences in hygroscopicity of

272 aerogels are reflected the hydrophobic modification can significantly reduce the hygroscopicity of

273 aerogel. In addition, the initial thermal decomposition temperature of aerogels ranges from 200℃ to

274 350℃. The polysaccharide base polymer network structure begins to depolymerize and the chain
275 structure breaks, resulting in a very significant weight loss region of aerogel at this stage (Abhari et al.

276 2017, Liang & Hirabayashi 1992). The mass loss rates of aerogel and hydrophobic aerogel were as high

277 as 34% and 12%, respectively, which showed significant differences. Then, the aerogels slowly loses

278 weight with the increase of temperature from 350℃ to 540℃, suggesting that the components in aerogels

279 are further thermologically decomposed. Moreover, the weight loss rate of the superhydrophobic

280 SA/CMC aerogel is always smaller than that of the SA/CMC aerogel. In addition, the temperature higher

281 than 540℃ is the carbonization stage of aerogel. With the increase of temperature, the trend of weight

282 loss rate curve of aerogels shows that polysaccharides and other components are completely thermal

283 degraded to form carbon oxides, and finally become inorganic components. The initial decomposition

284 temperature of the superhydrophobic SA/CMC aerogel increased from 250 °C of the SA/CMC aerogel

285 to 270 °C, and the maximum decomposition temperature also increased from 269 °C of the SA/CMC

286 aerogel to 326 °C. It indicated that the reduction in crystallinity after hydrophobic modification has little

287 effect on the increase of the thermal stability of the superhydrophobic SA/CMC aerogel. Besides,

288 Ca2+ crosslinking can form a 3D network with a unique “egg-box” structure upon ionic crosslinking. SA

289 and CMC produce strong chemical bonds with MTMS and Ca 2+ leading to a tighter and more solid

290 structure. Thus, the relatively high thermal stability appeared in superhydrophobic SA/CMC aerogel.
 1.2
TGA/DTG-SA/CMC aerogel
100 TGA/DTG-Superhydrophobic SA/CMC aerogel
270 ℃

Deriv.Weight (%/℃)
0.9
80

Weight (%)
250 ℃
366 ℃
60 332 ℃ 0.6
269 ℃

40
326 ℃
91 ℃ 0.3
452 ℃
20
83 ℃ 0.0
0
200 400 600 800
Temperature (℃)
291
292 Fig. 4. Thermogravimetric analysis of the SA/CMC aerogel and the superhydrophobic SA/CMC aerogel

293 about TGA curves and DTG curves.

294 3.3. Functionalities of the superhydrophobic SA/CMC aerogel

295 The porosities of the aerogels are decreasing with the increase of polysaccharide concentration in

296 Fig 5a. This trend is contrary to the density of the aerogels curve. The porosities of the SA/CMC aerogel

297 and the superhydrophobic SA/CMC aerogel are 97.64% and 94.16%, respectively. The densities of the

298 SA/CMC aerogel and the superhydrophobic SA/CMC aerogel are 0.03129 and 0.0794 g/cm3,

299 respectively. Fig 5b indicating the superhydrophobic SA/CMC aerogel can stand on the top of flower

300 stamens and dried flower because it's light enough.

 a 0.20 100

0.16
95

Density (g/cm3)

Porosity (%)
0.12 SA/CMC aerogel
Superhydrophobic SA/CMC aerogel 90
0.08

85
0.04

0.00 80
1.0 1.5 2.0 2.5
Concentration (wt%)
301

302

303 Fig.5. (a) Density and porosity of the SA/CMC aerogel and the superhydrophobic SA/CMC aerogel with

304 various concentration. Data are mean ± SD (n = 3); (b) Optical images indicating the superhydrophobic

305 SA/CMC aerogel can stand on the top of flower stamens and dried flower.

306

307 The perfect skeleton structure of aerogel can enhance its mechanical strength. Moreover, it plays an

308 important role in the process of oil adsorption and storage and oil-water separation. The compressive

309 stress-strain curves for the SA/CMC aerogel and the superhydrophobic SA/CMC aerogel are exhibited

310 in Fig. 6. The aerogels show different curves, indicating that the addition of SiO2 nanoparticles and

311 hydrophobic modification influence the mechanical property of the SA/CMC aerogel. The

312 superhydrophobic SA/CMC aerogel could be compressed to more than 80% without mechanical failure

313 due to the flexibility of CMC and SA with Ca2+ crosslinking. The appropriate compressive stress would
314 be beneficial to the integrity maintenance in practical applications (Zhou et al. 2018).

0.6

SA/CMC aerogel
0.4
Stress (MPa)
Superhydrophobic SA/CMC aerogel

0.2

0.0
0 20 40 60 80
Strain (%)
315
316 Fig.6. Compressive stress-strain curves of the SA/CMC aerogel and the superhydrophobic SA/CMC

317 aerogel with strain of 80%.

318

319 The effect of each step in the hydrophobic modification process on the water stability of aerogels is

320 shown in Support Information S2. Benefiting from the high surface roughness and polysaccharide

321 matrix with porous structure, the superhydrophobic SA/CMC aerogel shows superhydrophobicity and

322 superoleophilicity (Zhou et al. 2018). The WCAs for aerogels are exhibited in Fig. 7. As expected, the

323 superhydrophobic SA/CMC aerogel was hydrophobic with a WCA of 161.5°, which could be ascribed

324 to adding silica nanoparticles and successful silanizing modification. Fig. 7a exhibits the aerogel could

325 leave the water droplets standing on its surface, while absorbing the chloroform droplet. As shown in

326 Fig. 7b and Support Information S3, the water contact angles (WCAs, °) of SA/CMC aerogel with

327 various concentration are 0°. All the hydrophobic modification steps promoted the hydrophobic

328 properties of aerogels. A remarkable increase of WCA up to 161.5° was achieved with a series of

329 hydrophobic modifications, demonstrating the superhydrophobicity of the obtained composite aerogels.
330 The hydrophobic properties of aerogels could be improved by increasing the concentration of

331 polysaccharide and silane reagent in the same proportion. A preliminary hydrophobic modification

332 process of silanization could be carried out in the sol-gel reaction process to improve the hydrophobicity

333 of the SA/CMC aerogel. The obtained aerogel with preliminary hydrophobic modification using silane

334 reagent has more stable structure and better performance after Ca2+ crosslinking. Further, surface plasma

335 treatment prompts the hydroxyl functional groups on SA and CMC on the surface of the aerogel can be

336 activated and exposed, which is conducive to thermochemical vapor deposition as the subsequent

337 hydrophobic modification of silanization. Besides, the water droplet would return to its original shape

338 immediately after leaving the surface of the aerogel. The resultant figures present that the

339 superhydrophobic and superoleophilic SA/CMC aerogel with good hydrophobicity and low water

340 adhesion ensured that the oil agent could permeate and move through it, which is good for the oil-water

341 separation performance.

342

343 Fig.7. (a) Optical images of the process of water contacting the surface of two kinds of aerogels and

344 water (blue) and chloroform (red) on the surface of them; (b)The water contact angles (WCAs, °) of the

345 SA/CMC aerogel and the superhydrophobic SA/CMC aerogel with two kinds of polysaccharide

346 concentrations in different processing stages when the water drops stabilized after falling (0.25 s). Data

347 are mean ± SD (n = 3).

348 Methylene blue (MB, C16H18ClN3S) is a widely used cationic dye, which can be selected as the

349 target dye pollutant (Kannan & Sundaram 2001). The superhydrophobic SA/CMC aerogel could be used

350 to adsorb the MB, and its equilibrium adsorption capacity increases with initial concentration. Support

351 Information S4 exhibits the correlation between the concentration of MB and its absorbance. As shown

352 in Fig. 8, under the three different initial concentrations of MB, the equilibrium adsorption capacities of

353 the superhydrophobic SA/CMC aerogel are 2.19 mg/g, 4.64 mg/g and 7.22 mg/g, and the dye removal

354 percentage are 71.59 %, 75.79 % and 78.63 %, respectively. The main reason is the electrostatic attraction

355 as the main force between aerogel and MB.

356

357 Fig.8. Optical images of the superhydrophobic SA/CMC aerogel and MB solution concentration changes

358 (a) before and (b, c) after adsorption. (d) MB removal percentage and equilibrium adsorption capacity

359 at different initial concentrations of MB.

360

361 According to the Fig. 9 and Table 1, it can be seen the R22 is greater than 0.999 that very close to

362 1, indicating that the experimental data are highly consistent with the curve fitted by the pseudo-second-

363 order model. The value of Qec2 is highly close to the Qee obtained from the actual experiment. Above all

364 can show that the superhydrophobic SA/CMC aerogel of MB adsorption dynamics behavior conforms to
365 the pseudo-second-order model. The adsorption rate of MB by the superhydrophobic SA/CMC aerogel

366 is linearly related to the mass of aerogel and the initial concentration of MB. The adsorption process is

367 mainly chemical adsorption, which is closely related to the chemical composition of aerogel. The process

368 of MB adsorption by the superhydrophobic SA/CMC aerogel could also be directly fitted to a continuous

369 curve with linear relationship by the intra-particle diffusion. The straight line that passes through the

370 origin and above it, indicating that the kinetic process of MB adsorption by aerogel is affected by both

371 intra particle diffusion and boundary layer diffusion. As depicted in Fig.9c, the boundary molecular layer

372 constant Cid as the intercept of the line is greater than 0, indicating that there is a rapid adsorption process

373 in the process of MB adsorption, where the slope of the line represents the diffusion rate constant in the

374 particle (Wu et al. 2009). Moreover, the higher the initial concentration of MB was, the lower the degree

375 of linear fit of the model became. Therefore, the adsorption process can be further refined into three

376 stages. The first stage is the surface adsorption stage within 30 min. The adsorption rate is the fastest and

377 the intra-particle diffusion rate is the largest. The main reason is that the high initial concentration of MB

378 and the high porosity of aerogel can quickly adsorb a large number of dye molecules in the solution. The

379 second stage mainly occurred the adsorption rate gradually slows down in the 30-90 min period. The dye

380 molecules gathered on the outer surface of aerogel would increase with time, and MB would diffuse in

381 the small pores inside aerogel. The third stage occurs after 90 min of adsorption. There are fewer dye

382 molecules in the solution. The active adsorption sites on aerogel surface decreased with the decrease of

383 MB concentration. Therefore, the adsorption rate is the slowest and the diffusion rate in particles is the

384 smallest at this stage. Finally, the adsorption equilibrium state will be reached.
385

386 Fig.9. The influence of time on adsorption of MB with different initial concentrations by the

387 superhydrophobic SA/CMC aerogel and the fitting curves of adsorption kinetics (a); fitting curve of

388 pseudo-second-order model (b); fitting curve of intra-particle diffusion (c).

389 Table 1. The adsorption kinetics parameters of the superhydrophobic SA/CMC aerogel for MB solutions

390 with different initial concentrations

Kinetic model C0（mg/L） K2 (g/mg min) Qec2 (mg/g) R22

10 0.044649 2.190916 0.99977

Pseudo-second-order 20 0.018212 4.682525 0.99963

30 0.014491 7.293414 0.99959

Kinetic model C0（mg/L） Kid (mg/g min1/2) Cid (mg/g) R32

10 0.07662 1.19477 0.9054

Intra-particle diffusion 20 0.19015 2.23771 0.82331

30 0.26109 3.97997 0.76405

391

392 The superhydrophobic SA/CMC aerogel is an ideal candidate for the sorption of organic pollutants

393 due to its high porosity, compressive stability and hydrophobicity. The superhydrophobic SA/CMC

394 aerogel has a certain weight and volume adsorption capacity for various oils and organic solvents are

395 6−12 g/g and 65%−80% in Fig. 10. It exhibits the oil droplet could be absorbed by the aerogel

396 immediately when it contacted the aerogel surface. The superhydrophobic SA/CMC aerogel

397 preferentially adsorbs to a layer of oils and organic solvents dyed red in the oil-water mixture, such as

398 paraffin liquid, chloroform and hexane. In particular, chloroform has the best effect in the selective

399 competitive adsorption process of the superhydrophobic SA/CMC aerogel in Support Information S5.

400 Chloroform (ρchloroform > ρwater, red) and hexane (ρhexane < ρwater, red) were selected as two kinds of oils and

401 organic solvents with opposite density compared with water (blue). In order to further demonstrate the

402 absorbing capability of the superhydrophobic SA/CMC aerogel in oil-water separation, various kinds of
403 organic solvents (e.g., chloroform and hexane etc.) were tested by a simple device in Fig.11. The oil/water

404 mixture can be separated by gravity. The organic solvents could slowly permeate the aerogel and the

405 water is remains on top of the aerogel in the syringe. The separation efficiency of chloroform is 58.27%

406 and the fluid flux of oil-water separation is 74.66 mm·s. The aerogel will form an oil layer in the lower

407 layer because it has a certain adsorption effect on the oil, which prevents the further penetration of water

408 to successfully realize the separation of the oil-water mixture. Moreover, the superhydrophobic SA/CMC

409 aerogel has a good separation effect on oil-water mixture retaining original structure after adsorption.

410 However, the separation effect of this filtration method is not good for oil with density less than water

411 (Fig.11b). The main reason is that the oil contacted with the aerogel can percolate down to be collected

412 in the bottle. But the oil that has been blocked by the water layer from contacting the aerogel eventually

413 unable to be filtered by gravity when the oil-water mixture is poured. The superhydrophobic SA/CMC

414 aerogel after adsorbing organic liquids could be recycled by mechanically squeezing out oils or drying

415 absorbed samples at above the boiling point, which avoids the pollution and realizes the recyclability of

416 organic solvents further.

417

418
419 Fig.10. (a) Mass and (b) volumetric adsorption capacity of the superhydrophobic SA/CMC aerogel for

420 different oils and organic solvents (ρchloroform=1.484 g/cm3, ρoil pumping =0.874 g/cm3, ρtoluene =0.866 g/cm3,
421 ρAE=0.7893 g/cm3, ρhexane =0.6594 g/cm3).

422

423 Fig.11 (a, b) Schematic diagram of oil-water mixture separation process.

424 Table 2. Separation effect of the superhydrophobic SA/CMC aerogel for chloroform /water mixture

Test ma/g mb/g V/mm3 A/mm2  t/s η/% F

1 2.9832 1.8545 1243.296 176.7146 10.03 62.16 70.57

2 2.9832 1.5304 1026.012 176.7146 12.61 51.30 73.21

3 2.9832 1.8302 1227.005 176.7146 11.55 61.35 80.20

Average 2.9832 1.7384 1165.438 176.7146 11.40 58.27 74.66

425

426 4 Conclusion

427 In this study, the superhydrophobic SA/CMC aerogel was successfully fabricated and demonstrated

428 the feasibility of an effective absorbent for targeting dye methylene blue (MB) and organic pollutants.

429 The advantages of aerogel also include a green preparation environment, and a mild modification method,
430 including silane reagent modification, Ca2+ crosslinking, surface plasma treatment, thermochemical

431 vapor deposition and freeze-drying methods. The obtained aerogel represented superior physical features,

432 including low density, high porosity, mechanical stability, superhydrophobicity, water stability and

433 stable adsorption capacity for dyes and organic solvents. Furthermore, it is found that the initial MB

434 concentration significantly affects the absorption capability of the aerogel. The pseudo-second-order

435 model and intra-particle diffusion are applied to describe and validate the MB absorption behavior of the

436 aerogel. Moreover, it could separate oil-water mixture without external pressure for various organic

437 solvents. Consequently, the superhydrophobic SA/CMC aerogel offers a great feasibility for various

438 applications in the fields of environment remediation, organic solvents purification and removal of

439 organic liquids from waterbody etc.

440 Declarations

441 Conflict of interest

442 The authors declare that they have no known competing financial interests or personal relationships

443 that could have appeared to influence the work reported in this paper.

444 Funding / Acknowledgments

445 We gratefully acknowledge the Support by the Opening Project of China National Textile and

446 Apparel Council Key Laboratory of Natural Dyes, Soochow University (No.SDHY2122), the National

447 Natural Science Foundation of China (No.31470509) and Jiangsu Natural Science Foundation for

448 General project (BK20191199).

449 Author Contribution

450 CRediT authorship contribution statement

451 Huiming Li: Conceptualization, Investigation, Data curation, Writing - original draft. Jingyi Huang:

452 materials preparation. Chaoran Meng and Shen Shen: review & editing. Hongbo Wang and Jiajia Fu:

453 review & editing; Supervision & Funding acquisition. All authors reviewed the manuscript.

454 Ethics approval and consent to participate

455 Not applicable

456 Consent for publication

457 All authors believe that the findings of this study are relevant to the scope of your journal and will be of

458 interest to its readership.

459 Availability of data and materials

460 The results/data/figures in this manuscript have not been published elsewhere, nor are they under

461 consideration (from all authors) by another publisher.

462 Authors' information (optional)

463 Huimin Li

464 Jiangnan University

465 1800 Lihu Avenue, Wuxi 214122, China

466 Tel: 0086-15764233420

467 Email Address: 7200707007@stu.jiangnan.edu.cn

468

469 Jingyi Huang

470 Jiangnan University

471 1800 Lihu Avenue, Wuxi 214122, China

472 Email Address: hjy364570266@163.com

473

474 Chaoran Meng

475 Jiangnan University

476 1800 Lihu Avenue, Wuxi 214122, China

477 Email Address: 8202101470@jiangnan.edu.cn

478

479 Shen shen

480 Jiangnan University

481 1800 Lihu Avenue, Wuxi 214122, China

482 Email Address: 7170707009@stu.jiangnan.edu.cn

483

484 Hongbo Wang

485 Jiangnan University

486 1800 Lihu Avenue, Wuxi 214122, China

487 Email Address: wxwanghb@163.com

488

489 Jiajia Fu

490 Jiangnan University

491 1800 Lihu Avenue, Wuxi 214122, China

492 Email Address: kathyfjj@126.com

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