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Article
New Amidoxime Based Material TMP-g-AO for
Uranium Adsorption under Seawater Conditions
Jiayun Zeng, Hui Zhang, Yang Sui, Nan Hu, Dexin Ding, Fang Wang, Jinhua Xue, and Yongdong Wang
Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.6b05006 • Publication Date (Web): 10 Apr 2017
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Page 1 of 42 Industrial & Engineering Chemistry Research

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4 1 New Amidoxime Based Material TMP-g-AO for Uranium Adsorption
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2 under Seawater Conditions
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9 3 Jiayun Zeng1, Hui Zhang1, Yang Sui2, Nan Hu1, Dexin Ding1,*, Fang Wang1, Jinhua
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11 4 Xue1, Yongdong Wang1
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14 5 1 Key Discipline Laboratory for National Defense for Biotechnology in Uranium
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16 6 Mining and Hydrometallurgy, University of South China, Hengyang 421001, China
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7 2 Hunan Taohuajiang Nuclear Power Co., Ltd, Yiyang, 413000, China
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38 18 *Corresponding author: Dexin Ding
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41 19 Key Discipline Laboratory for National Defense for Biotechnology in Uranium
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43 20 Mining and Hydrometallurgy, University of South China, 28 West Changsheng
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45 21 Road, Hengyang, Hunan 421001, People’s Republic of China.
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47 22 E-mail: zh2015yl@163.com (Dexin Ding);
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50 23 Jiayun Zeng and Hui Zhang contributed equally to this work.
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3 1 ABSTRACT: A novel amidoxime based adsorbent of titanium-
4
5 2 molybdopyrophosphate-g-amidoxime (TMP-g-AO) was prepared by chemical
6
7 3 co-precipitation and subsequent chemical modifications. The successful grafting of
8
9 4 acrylonitrile group and the subsequent conversion of acrylonitrile group to amidoxime
10
11 5 groups were characterized by Scanning Electron Microscopy-Energy Disperse
12
13 6 Spectroscopy, Fourier Transform Infrared Spectroscopy, X-ray Photoelectron
14
15 7 Spectroscopy, N2-BET and Thermal analysis. The adsorption behavior of uranium(VI)
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17 8 on TMP-g-AO was investigated for low concentration uranium solution by batch
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9 experiments at a fixed pH 8.2±0.1. It is found that the adsorption rate of uranium from
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20 10 solution was 99.77% when the uranium concentration was 42.3 µg/L, pH, 8.2±0.1,
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22 11 temperature, 298.15 K, and the adsorbent dosage, 0.05 g. The kinetic data follow the
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24 12 pseudo-second-order model and adsorption equilibrium data fit the Langmuir model
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26 13 well. The thermodynamics parameters (∆S, ∆H and ∆G) indicate that the adsorption
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28 14 process is spontaneous and endothermic. The functional TMP-g-AO adsorbent
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30 15 exhibits good selectivity and affinity for uranium ions under coexisting multi-metal
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32 16 ions except for Fe3+ and Co2+. Desorption was performed and the adsorption rate of
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34 17 uranium by TMP-g-AO only decrease 1.42% after five consecutive
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18 adsorption-desorption cycles. In order to evaluate the potential application of
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37 19 TMP-g-AO for uranium extraction from seawater, the experiments on adsorption of
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39 20 uranium(VI) from natural seawater and the uranium-doped seawater were conducted
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41 21 and the adsorbent exhibited high adsorption rate of uranium(VI). The results show
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43 22 that the TMP-g-AO could be a very promising adsorbent for uranium extraction from
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45 23 seawater.
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47 24 KEYWORDS: uranium(VI); amidoxime; adsorption; seawater
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4 1 . INTRODUCTION
1.
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6 2 Nowadays, the traditional oil, coal and other nonrenewable fossil fuels are being
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8 3 gradually consumed, which brings out various social and environmental problems.1
9
10 4 There has been a consensus throughout the world that people should try their best to
11
12 5 adjust the energy structure, improve the efficiency of energy, develop green energy and
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14 6 achieve the sustainable development of economic and environment. Uranium is used as
15
16 7 a nuclear fuel to produce nuclear energy and the nuclear energy is considered as one of
17
8 the most environmentally friendly energies. According to a recent estimate, terrestrial
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19 9 uranium reserves can only guarantee uranium supply for nuclear power production for
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21 10 100 years. To ensure the long-term development of nuclear power production, it is
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23 11 crucial to exploit nonconventional uranium resources, such as uranium in seawater.
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25 12 There areapproximately 4.5 billion tons of uranium in the oceans, nearly 1000 times
26
27 13 greater than the terrestrial uranium reserves.2 However, efficient and selective
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29 14 extraction of uranium from seawater is particularly challenging because of high
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31 15 salinity, high carbonate concentration, basic pH (7.9 ~8.4), low uranium concentration
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33 16 (∼3.3 ppb) and other metal ions at similar or higher concentrations in seawater.3,4
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17 Up to now, a variety of approaches, such as solvent extraction, ion-exchange,
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36 18 membrane separation, nano-filtration and adsorption, have been developed to
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38 19 concentrate uranium from seawater.5-8 Solvent extraction has been successfully used to
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40 20 separate uranium from seawater. However, it has a number of drawbacks such as long
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42 21 time operation and large organic solvent consumption. For ion exchange method, the
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44 22 ion exchange capacity and cycle efficiency are very low. Furthermore, the exchangers
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46 23 are susceptible to saturation and regeneration is difficult. Membrane separation
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48 24 processes have been used for several years to concentrate or fractionate suspended
49
50
25 particles and dissolved species,9 which are prone to membrane fouling and membrane
51 26 specificity needs to be further studied. Nano-filtration is influenced by the size of
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53 27 separated species and pressures which may limit its application in the field of uranium
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55 28 extraction from seawater. Adsorption, due to its high efficiency and ease of handling,
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57 29 has been employed for the removal of uranium from nuclear industrial effluents, mine
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59 3
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3 1 water and seawater10 and it is considered as one of the most promising techniques for
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5 2 uranium pre-concentration from seawater.
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7 3 Many types of adsorbents have been studied for the recovery of uranium from
8
9 4 seawater, such as metal oxide,11-16 chitosan resin,17-19 metal-organic framework,20
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11 5 layered metal sulfides21,22 and amidoxime based adsorbents.23-25 Amidoxime based
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13 6 adsorbents have attracted intensive attention since the 1960s due to the high
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15 7 selectivity and affinity to uranium. Amidoxime based adsorbents adsorb metal ions
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17 8 owing to lone-pair electrons in electron donating groups (–NH2, HNCH3, and N(CH3)2),
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9 which form coordination bond and stable structure with metal ions.26 In many cases,
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20 10 those amidoxime-functionalized materials can be synthesized by introducing
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22 11 acrylonitrile groups (–CH2–CH–C≡N) into solid structures and then converting these
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24 12 groups to amidoxime groups (–CH2–CH–C(NH2)＝NOH)3. For instance, Xu et al.
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26 13 prepared amidoximed chitosan-grafted poly-acrylonitrile (CTS-g-PAO) via
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28 14 precipitation graft copolymerization of chitosan and acrylonitrile, and then converted
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30 15 the acrylonitrile groups into amidoxime ones using hydroxylamine hydrochloride.27
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32 16 These combinations of chitosan and amidoxime groups had their respective advantages
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34 17 complementary to each other. Das et al. synthesized a new series of amidoxime-based
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18 polymer adsorbents using electron beam induced grafting of acrylonitrile and itaconic
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37 19 acid onto polyethylene fiber.28 And the synthetic DMSO-heat-treated sorbents
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39 20 adsorbed uranium as high as 4.48 g-U/kg-ads from seawater. Shen et al. reported that
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41 21 the PAN/MMT nanocomposite was prepared through in-situ intercalation
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43 22 polymerization, and the uranium adsorption capacity reached up 3.06 mg/g at pH 7.54
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45 23 Lu et al. prepared the C8A-AO adsorbent which exhibited excellent selective
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47 24 adsorption capacity of 98.425 mg/g at pH 7 for uranium ions in simulated seawater.55
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49 25 These studies demonstrated that the amidoxime group has strong affinity and can
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26 chelates effectively the uranyl tricarbonate complexes [UO2(CO3)34－] in neutral or
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27 weakly alkaline solution. Therefore, the amidoxime based adsorbents are considered
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54 28 as the most promising materials for adsorption of uranium from seawater. In addition,
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56 29 some pyrophosphate adsorbents exhibit a large adsorption capacity for uranium ions
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58 30 in aqueous solution. The maximum adsorption capacity of ZMPP-TBP for
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3 1 uranium(VI) was 196.08 mg/g at 293 K and pH 6.52 Likewise, Wang et al.53 prepared
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5 2 pyrophosphate Zr1-xTixP2O7 and TiP2O7 by microwave-induction, and the maximum
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7 3 amount of the uranium on TiP2O7 reached up to 309.8 mg/g under the experimental
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9 4 conditions (pH=5, t=60 min and T=303 K). These pyrophosphate adsorbents generally
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11 5 have a large specific surface area and may be used for immobilization and long-term
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13 6 storage of uranium ions due to the properties of near zero or negative thermal
14
15 7 expansion. In summary, the inorganic bimetallic pyrophosphate, as a base material,
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17 8 grafts with amidoxime group which can compensate for the shortcoming of instability,
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9 and the synthetic adsorbents tend to have a good surface reactivity.
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20 10 In this work, a new amidoxime based adsorbent Titanium-
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22 11 molybdopyrophosphate-g-amidoxime (TMP-g-AO) was fabricated by chemical
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24 12 coprecipitation and subsequent chemical modifications. The successful grafting of
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26 13 acrylonitrile groups on the surface of TMP-g and the subsequent converting of
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28 14 acrylonitrile groups to amidoxime groups were characterized by Scanning Electron
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30 15 Microscopy-Energy Disperse Spectroscopy (SEM-EDS), Fourier Transform Infrared
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32 16 Spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), N2-BET and Thermal
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34 17 analysis. The uranium adsorption behavior of TMP-g-AO was investigated for the first time.
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18 The influences of different factors, such as adsorbent dosage, initial uranium
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37 19 concentration, contact time, temperature and coexisting ions, on uranium(VI)
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39 20 adsorption were investigated by batch experiment at fixed pH 8.2±0.1. Sorption
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41 21 isotherms of uranium(VI) were illustrated by Langmuir and Freundlich patterns. The
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43 22 kinetic experimental data were simulated by pseudo-first-order and
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45 23 pseudo-second-order models and the kinetic parameters were determined. In order to
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47 24 evaluate the potential application of TMP-g-AO for uranium extraction from seawater,
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49 25 the adsorption of uranium(VI) from natural seawater (3.65µg/L) and the
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26 uranium-doped seawater (61.02µg/L) was conducted.
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53 27 2. EXPERIMENTS
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28 2.1. Materials. Acrylonitrile (AN), hydroxylamine hydrochloride (NH2OH·HCl),
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57 29 N,N-dimethylformamide (DMF), silane coupling agent (KH-570),
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59 5
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3 1 2,2-Azobisisobutyronitrile (AIBN), titanium tetrachloride (TiCl4), phosphormolybdic
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5 2 acid (H3PO4·12MoO3), potassium pyrophosphate trihydrate (K4P2O7·3H2O),
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7 3 ethanol, ammonia (25%), sodium carbonate and hydrochloric acid (36%) were
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9 4 purchased from Tianjin Kermel Chemical Reagents Development Center (Tianjin,
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11 5 China). All of these chemicals were analytic grade reagents without further
12
13 6 purification.
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15 7 The stock solutions of uranium(VI) (1.0g/L) were prepared in the following
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17 8 procedure: 1.1792 g U3O8 powder was first dissolved in hydrochloric acid (10 mL),
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9 hydrogen peroxide (3 mL) and two drops of nitric acid by heating in the sand bath; and
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20 10 the mixture was then cooled to room temperature and diluted with ultrapure water to
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22 11 1000 mL, which was the standard solution of uranium. The solutions with different
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24 12 uranium(VI) concentrations for experiments were prepared by diluting the stock
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26 13 solution using ultrapure water.
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28 14 2.2. Preparation of the TMP-g-AO adsorbent. TMP-g-AO adsorbent was prepared
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30 15 by chemical co-precipitation and subsequent chemical modifications. The preparation
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32 16 process of TMP-g-AO consists of four steps and is illustrated in detail in Figure S1.
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34 17 (i) Synthesis of TMP by chemical co-precipitation: Firstly, equimolar amounts of
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18 potassium pyrophosphate trihydrate and phosphomolybdic acid solutions were mixed
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37 19 with a ratio of 10:1 (v/v), and the pH of the mixture was adjusted to 2~3. Then, the
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39 20 solution of titanium tetrachloride was added dropwise to the flask under stirring until no
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41 21 more white precipitation appeared. After centrifuging and discarding the supernatant
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43 22 liquor, the sediment obtained was washed with ethanol several times and then dried in a
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45 23 vacuum oven overnight at 333.15 K.
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47 24 (ii) Modifying TMP with silane coupling agent KH-570 (TMP-g): 6.0 g of the
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49 25 dried TMP was immersed in ethanol (120 mL) and deionized water (6.5 mL), and then
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26 4 mL of 25 wt% aqueous ammonia and 2 mL of silane coupling agent KH-570 were
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27 added. The mixture was stirred continuously at 328.15 K for 48 h. After filtration, the
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54 28 sediment was repeatedly washed with ethanol to remove residual KH-570 and dried in
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56 29 a vacuum oven overnight at 333.15 K.
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58 30 (iii) Grafting acrylonitrile on the surface of TMP-g: First, 1.5 g of TMP-g and 100
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3 1 mL solvent of N,N-dimethylformamide (DMF) were added in three-necked round
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5 2 bottom flask (with reflux condenser and thermometer), and the mixture was heated in a
6
7 3 water bath to 343.15 K under N2 flow and magnetic stirring of 1000 r/min. Then, 12 mL
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9 4 of acrylonitrile (including 0.15 g of 2,2-azobisisobutyronitrile) was added to the
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11 5 mixture by syringe, the mixture was kept in N2 atmosphere at 343.15 K for 5 h, and the
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13 6 product of TMP-g-AN was collected by centrifugation and then washed with ethanol
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15 7 several times to remove the residual DMF. Finally, the product was dried overnight at
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17 8 333.15 K.
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9 (iv) Converting acrylonitrile to amidoxime (TMP-g-AO): First, 1.5 g of
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20 10 TMP-g-AN, together with 160 mL of water/ethanol (3v/1v) and 1.0 g of sodium
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22 11 carbonate, was added in four-necked round bottom flask (with reflux condenser and
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24 12 thermometer), and the mixture was heated in a water bath to 343.15 K under N2 flow
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26 13 and magnetic stirring of 1000 r/min. Then, 1.39 g of hydroxylamine hydrochloride
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28 14 (dissolved in 5 mL of water) was slowly added to the mixture by syringe, the mixture
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30 15 kept in N2 atmosphere at 343.15 K for 5 h, and the yellow product of TMP-g-AO was
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32 16 collected by centrifugation and then washed with ethanol three times. Finally, the
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34 17 product was dried overnight at 333.15 K.
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18 2.3. Instruments. A field emission scanning electron microscope equipped with
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37 19 Energy Disperse Spectroscopy (SEM-EDS, Raith ELPHY Quantum Electron
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39 20 Lithography (kit), Raith, USA) was used to characterize the morphologies of the
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41 21 synthetic products. Fourier Transform Infrared spectroscopy (FT-IR, NicoletiS10,
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43 22 Thermo Scientific, USA) was used to evaluate the change in the structure of the
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45 23 synthetic products. X-ray photoelectron spectroscopy (XPS, ESCALAB 250Xi,
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47 24 Thermofisher-VG Scientific, USA) of the TMP-g-AO and TMP-g-AO –U powders
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49 25 were measured using a Thermo Scientific ESCALAB 250 Xi spectrometer equipped
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51
26 with a monochromatic Al Kα X-ray source (1486.6 eV) operating at 300 W. The
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27 concentrations of uranium (VI) in solutions were measured by Inductively Coupled
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54 28 Plasma Mass Spectrometry (ICP-MS, 7700X, Agilent, USA).
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56 29 2.4. Batch Adsorption Experiments. The TMP material is dissolvable in solution, and
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58 30 the materials of TMP-g, TMP-g-AN, and TMP-g-AO are insoluble and stable in
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3 1 distilled water and hydrochloric acid (0.1 M). The adsorption experiment of uranium
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5 2 ions was respectively carried out by TMP-g, TMP-g-AN, and TMP-g-AO (m=0.05 g,
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7 3 C0=53.83 µg/L, V=50 mL, pH=8.2±0.1, T=298.15 K, t=120 min), and the adsorption
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9 4 rates of TMP-g, TMP-g-AN, and TMP-g-AO are respectively 58.37%, 69.16% and
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11 5 98.94% which have a big difference. Therefore, we only studied the adsorption
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13 6 behavior of TMP-g-AO by batch adsorption in the next experiment.
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15 7 Batch adsorption experiments were carried out to investigate the effects of
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17 8 adsorbent dosage, initial uranium concentration, contact time, temperature and
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9 coexisting ions on uranium(VI) adsorption. Considering the practical application of
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20 10 uranium adsorption from seawater, the pH of uranium(VI) solution was adjusted to
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22 11 8.2±0.1 with 0.1 M HCl and Na2CO3 solutions. All experiments were conducted by
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24 12 mixing 50 mL of uranium(VI) ion solutions with 0.05 g of TMP-g-AO adsorbent in
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26 13 conical flasks, followed by shaking in a constant temperature shaker at 180 rpm for a
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28 14 given time at 288.15~333.15 K. After that, 5 mL of the mixture was filtered by 0.22 µm
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30 15 syringe filter and then soured by concentrated nitric acid. The mixture was used to
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32 16 analyze the residual concentration of uranium(VI) by ICP-MS. All the experiments
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34 17 were performed in duplicates and a blank sample was set at the same time to minimize
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18 experimental error. Finally, the data were analyzed by origin software (Version 8.0,
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37 19 USA).
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39 20 The adsorption capacity Q (µg/g), adsorption rate Ads% and distribution
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41 21 coefficient K  (mL/g) were calculated using the following formulas.
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43  −  ) × 
 = 1)
44 
45  −  )
46 % = × 100 2)
47

48  −  1000
 = × 3)
49  
50
51
22 Where C and C are the initial and equilibrium concentrations of uranium(VI) (µg/L),
52
23 respectively; V is the volume of testing solution (L); and m is the amount of the
53
54 24 adsorbent (g).
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56 25 2.5. Desorption and Regeneration Studies. To evaluate the stability and reusability of
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58 26 TMP-g-AO material, the adsorption and regeneration were performed in five
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3 1 consecutive cycles. In each cycle, 0.05 g of adsorbent was shaken with 50 mL of
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5 2 uranium(VI) solution for a given time at 298.15 K. After that, adsorbent loaded with
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7 3 uranium(VI) was eluted using desorption solution (50 mL 0.1 M HCl), and washed
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9 4 with large amount of ultrapure water. Then, it was reused for uranium adsorption as
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11 5 before. The desorption rate DE% was calculated using the following formula.
12

13 #$% = × 100 4)
14  − 
15 6 Where C (µg/L) is the concentration of uranium(VI) in solution after desorption;
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17 7 and C (µg/L)and C (µg/L) are the initial and equilibrium concentrations of uranium
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19 8 (VI), respectively.
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21 9
22
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24
10 3. RESULTS AND DISCUSSION
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26 11 3.1. Characterization
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28 12 3.1.1. Scanning Electron Microscopy and Energy Disperse Spectroscopy. The
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30 13 scanning electron microscopy is widely used to investigate the morphological features
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32 14 and surface characteristics of the adsorbent materials.29 SEM was used to observe
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34 15 morphologies of TMP (a), TMP-g (b), TMP-g-AN (c), TMP-g-AO (d) and
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36 16 TMP-g-AO-U (e), and to compare their differences. As is shown in Figure 1, it is
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17 clear that the diameters of samples are of nanoscale. In Figure 1(a), the TMP sample
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39 18 presents a spherical shape and a smooth surface. After TMP-g is modified with
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41 19 KH-570, the surface of TMP-g particles becomes rough. Furthermore, a dense
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43 20 structure can be seen and much irregular matter has been generated between spherical
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45 21 particles in Figure 1(c, d). These changes in the surface appearance of TMP-g-AN and
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47 22 TMP-g-AO samples are due to the grafting and oximation. The surface of
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49 23 TMP-g-AO-U are also rough and dense, as shown in Figure 1(e), and the surface of
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51 24 TMP-g-AO is covered with many small particles which may be due to the adsorption
52
53 25 of uranium ions. The chemical compositions of the TMP-g-AO and TMP-g-AO-U
54
26 obtained by the EDS analysis are shown in Figure 1(f, g) and Table S1. In comparison,
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56 27 uranium ion is adsorbed on the surface of the material and the atomic percentage of U
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3 1 is 1.75% after adsorption. However, the atomic percentages of both N and O elements
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5 2 decrease, which may be attributed to the reaction between amidoxime groups and
6
7 3 uranium ions.
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9 4 3.1.2. Fourier Transform Infrared Spectroscopy. The Fourier Transform Infrared
10
11 5 Spectroscopy of TMP (a), TMP-g (b), TMP-g-AN (c), TMP-g-AO (d) and
12
13 6 TMP-g-AO-U (e) materials are shown in Figure 2, and the characteristic peaks of –
14
15 7 OH and –P–O at 3582 and 1564 cm-1 can be observed in the curve of TMP. After
16
17 8 surface modification of TMP by KH-570, the peak of –OH disappears and the new
18
9 characteristic peaks at 3161, 1406, 1178 and 885 cm-1occur respectively in the curve of
19
20 10 TMP-g, which is attributed to the groups of –CH2–,–Si–O–,–C–O– and –C=C–.
21
22 11 Additionally, in the curve of TMP-g-AN, a sharp peak at 2242 cm-1 is assigned to –
23
24 12 C≡N– and the peak of –C=C– at 885 cm-1 disappears owing to the polymerization
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26 13 between –C=C– and acrylonitrile.30 In the curve of TMP-g-AO, the new characteristic
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28 14 peaks for –NH2 (or –OH), –C=N–, –C–N– and –N–O– appear respectively with
29
30 15 wavenumbers at 3194, 1649, 1269 and 920 cm-1.31-33 Meanwhile, the peak at 2242 cm-1
31
32 16 related to –C≡N– disappears and the peak of –C=N– increases sharply, which
33
34 17 indicates that the nitrile group was converted completely into the amidoxime group
35
18 after reaction with hydroxylamine hydrochloride. In addition, the peak of –N–O–
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37 19 moves from 920 cm-1 to 913 cm-1, and changes in peak positions and intensity around
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39 20 550-1000 cm-1 region in the curve of TMP-g-AO-U can be assigned to asymmetric
40
41 21 stretching vibration of uranyl ion and stretching vibrations of weakly bonded oxygen
42
43 22 ligand with uranium.50,51
44
45 23 3.1.3. X-ray Photoelectron Spectroscopy. The chemical bonding states on the
46
47 24 surface of the samples are further investigated by XPS. By comparing the element
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49 25 contents of TMP-g-AO with those of TMP-g-AO-U in Table S2, it can be found that
50
51
26 the contents of C1s and O1s increase from 38.29% to 39.46% and from 33.20% to
52
27 35.25% after adsorption, respectively. However, the N1s content decreases from 16.77%
53
54 28 to 10.85%, the reason of which may be that the surface of the synthetic adsorbent is
55
56 29 heterogeneous, and uranium adsorbed on the surface of the TMP-g-AO material
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58 30 affects the elemental analysis since the analysis depth of XPS is generally from 2 to 5
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3 1 nm. Therefore, the C/N ratio increases obviously from 2.28 to 3.64. As shown in
4
5 2 Figure 3, the U4f5/2 and U4f7/2 peaks appear with the binding energies at 392.24 and
6
7 3 381.39 eV,34-37 and the U4f content reaches 2.29%. In addition, the C1s and N1s
8
9 4 spectra of the TMP-g-AO sample before and after uranium adsorption are shown in
10
11 5 Figure 4. The C1s of TMP-g-AO consist of the CO32-, C-O, H2N-C=N-OH and
12
13 6 C-C(C-H) at 288.34, 287.09, 285.89 and 284.50eV, respectively.38 The N1s can be
14
15 7 curve-fitted with two peaks at 399.19 and 400.64 eV for H2N-C=N-OH and
16
17 8 H2N-C=N-OH.39 After adsorption, the peak comprised of CO32-, C-O, H2N-C=N-OH
18
9 and C-C(C-H) at 288.35, 287.25, 286.08 and 284.69 eV can fit well with the C1s
19
20 10 curve of TMP-g-AO-U. And the N1s can also be fitted with H2N-C=N-OH and
21
22 11 H2N-C=N-OH peaks at 399.41 and 401.29 eV.40 In conclusion, the XPS analysis can
23
24 12 further confirm the FT-IR and EDS results.
25
26 13 3.1.4. N2-BET Analysis. The structural properties of the synthesized TMP-g-AO
27
28 14 material can be analyzed by the nitrogen adsorption-desorption isotherm. As shown in
29
30 15 Figure 5, the isotherm of TMP-g-AO firstly presents a steep increase in adsorption
31
32 16 which attributes to the characteristic of microporous materials, and then there is a
33
34 17 smoother hysteresis loops at relative pressures of 0.4~1.0 due to the nitrogen
35
18 condensation in the mesoporous. Therefore, the isotherm of TMP-g-AO seems to be
36
37 19 nearly type IV with a H4 hysteresis loop according to the IUPAC classification. The
38
39 20 BET surface area, pore volume and average pore diameter are calculated from the
40
41 21 appropriate section of the adsorption-desorption isotherm and the values of them are
42
43 22 48.183 m2/g, 0.116 cm3/g and 3.911 nm, respectively. Obviously, the pore volume of
44
45 23 TMP-g-AO is very small due to their dense surface, which is also confirmed by the
46
47 24 results from SEM.
48
49 25 3.1.5. Thermal Analysis. The TGA and DTG characterization was carried out to study
50
51
26 the thermal stability of TMP-g-AO adsorbent in an argon atmosphere. As can be seen
52
27 from Figure 6, the weight loss of 4.84% at ~120 °C can be assigned to the loss of
53
54 28 adsorbed moisture. Then, the TMP-g-AO sample has a 13.74% weight loss at
55
56 29 120~340 °C, which may be attributed to the decomposition of the amidoxime
57
58 30 groups.55 At last, the weight loss is about 11.07% due to the complete degradation and
59 11
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2
3 1 decomposition of the polymerized amidoxime group when the temperature is above
4
5 2 340 °C.57 Therefore, the mass ratio of the polymerized amidoxime group to TMP-g
6
7 3 and the weight percent of the polymerized amidoxime group in dry TMP-g-AO are
8
9 4 0.423:1 and 29.7%, respectively. This result provides further evidence that the
10
11 5 TMP-g-AO adsorbent is successfully prepared.
12
13 6
14
15 7 3.2. Uranium(VI) Adsorption Performance
16
17 8 3.2.1. Effect of Adsorbent Dosage. The adsorbent dosage is one of most important
18
19 9 factors that influence the adsorption equilibrium. Adsorbent dosages ranging from 0.01
20
21 10 to 0.08 g were used to investigate the effect of adsorbent dosage on the adsorption
22
23
11 behavior of the TMP-g-AO at a fixed pH value of 8.2±0.1and temperature of 298.15
24
12 K. As shown in Figure 7, the adsorption rate of uranium(VI) increases rapidly with the
25
26 13 increase of TMP-g-AO dosage when it is lower than 0.02 g, and then remains almost
27
28 14 constant. However, the adsorption capacity decreases continuously for the reason that
29
30 15 the amount of uranium ions adsorbed per unit mass of TMP-g-AO is reduced. With
31
32 16 the increase of TMP-g-AO dosage, the available adsorption sites on adsorbent surface
33
34 17 increase and thereby the amounts of uranium(VI) ions in aqueous solution will be
35
36 18 further decreased.
37
38 19 3.2.2. Effect of Coexisting Ions. In order to evaluate the selectivity of the TMP-g-AO
39
40
20 adsorbent, the influence of coexisting ions (such as V5+, Fe3+, Ni2+, Cu2+, Pb2+, Zn2+
41 21 and Co2+) on uranium adsorption was studied according to some related literature.41-43
42
43 22 The concentrations of coexisting ions in actual adsorption tests were designed by
44
45 23 taking into account of the concentrations of these ions in natural seawater and
46
47 24 presented in Table S3. The concentrations of V5+ and Ni2+ are close to those in natural
48
49 25 seawater, but the concentrations of other ions are several tens and thousands times
50
51 26 higher than those in natural seawater. The selectivity coefficient and distribution
52
53 27 coefficient of ions are determined after the adsorption reaches equilibrium. As shown
54
55 28 in Figure 8, it is obvious that the selectivity of TMP-g-AO for the coexisting ions is in
56
57
29 the order of U6+>Fe3+>Co2+>Pb2+>Ni2+>Zn2+>V5+>Cu2+. Moreover, the values of
58
59 12
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2
3 1 selectivity coefficient for coexisting ions are greater than 2 except for Fe3+ and Co2+,
4
5 2 suggesting that Fe3+ and Co2+ may be adsorbed onto TMP-g-AO with uranium(VI) ion
6
7 3 at the same time. Therefore, the functional TMP-g-AO adsorbent still has very good
8
9 4 selectivity and affinity for uranium ions under coexisting multi-metal ions except for
10
11 5 Fe3+ and Co2+.
12
13 6 3.2.3. Effect of Contact Time and Adsorption Kinetics. The effect of contact time on
14
15 7 the adsorption of uranium(VI) ions onto the TMP-g-AO was investigated for three
16
17 8 different initial uranium concentrations (42.3, 104.8 and 226.5 µg/L) and the results
18
9 are shown in Figure 9. It is clear that the adsorption of uranium(VI) ions consists of two
19
20 10 steps: a relatively rapid step and a subsequent slow step. The adsorption rate of
21
22 11 uranium(VI) ions increases rapidly in the first 30 min and then increases gradually until
23
24 12 the adsorption process achieves equilibrium after 300 min. The first rapid step may be
25
26 13 due to the surface physical sorption and chemical reactive sorption. However, the
27
28 14 subsequent slow step may be attributable to the reactive adsorption of the inner
29
30 15 polymer chain segments.40
31
32 16 In order to study the adsorption kinetics of uranium(VI) on TMP-g-AO in aqueous
33
34 17 solutions, two kinetic models (pseudo-first-order and pseudo-second-order kinetic
35
18 models) were used to investigate the kinetic mechanism of adsorption processes
36
37 19 between adsorbent and adsorbate.
38
39 20 The pseudo-first-order kinetic model is expressed as:
40
41 )*
42
ln − ( ) = ln − × , 5)
2.303
43
44 21 The pseudo-second-order kinetic model is expressed as:
45 , 1 ,
46 = .
+ 6)
( ). ×  
47
48 22 Where Q (µg/g) and Q1 (µg/g) are the adsorption capacities at equilibrium and time t
49
50 23 (h), respectively;k* (h-1) and k . (h-1) are the rate constant of pseudo-first-order and
51
52 24 pseudo-second-order models for the adsorption uranium(VI), respectively.
53
54 25 The kinetic parameters such as k* , k . , Q and correlation coefficient (R2), can be
55
56 26 calculated from the linear form of models in Figures S2a and b and the results are
57
27 shown in Table 1. The values of Q increase obviously with the increase of the initial
58
59 13
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2
3
1 uranium concentration. Moreover, the values of Q and R2 for the pseudo-second-order
4
5 2 kinetics are higher than those for the pseudo-first-order kinetics. Therefore, the kinetic
6
7 3 behavior of uranium adsorption onto TMP-g-AO can be described by the
8
9 4 pseudo-second-order kinetic model. This indicates that chemical adsorption might be
10
11 5 the controlling step which may involve valence forces through sharing of electrons
12
13 6 between uranium(VI) ions and adsorbent.44
14
15 7 3.2.4. Effect of Initial Uranium Concentration and Adsorption Isotherm. The initial
16
17 8 uranium concentration provides an important driving force to overcome all mass
18
9 transfer resistance of uranium between the aqueous and solid phases.4 The experiment
19
20 10 on adsorption of uranium(VI) on TMP-g-AO adsorbent was carried out in various
21
22 11 concentrations and the contact time was long enough (3 days) to ensure that the
23
24 12 adsorption of uranium reached equilibrium. The results are shown in Figure 10. The
25
26 13 adsorption capacity firstly increases linearly with initial uranium concentration and
27
28 14 then it almost tends to equilibrium.
29
30 15 The adsorption isotherm reflects on the relation between the adsorption capacity
31
32 16 and uranium concentration when the adsorption process reaches equilibrium. The
33
34 17 adsorption data have been measured to simulate different adsorption isotherms
35
18 including Langmuir and Freundlich models. The Langmuir model is based on
36
37 19 assumption of homogenous adsorption and its basic equation can be expressed as:
38
39 3 4 5
40 Q = = 7)
 1 + 5 )
41
42 20 The standard form of linear equation can be derived from equation (7) as follows:
43  1 
44 = + 8)
45  4 5 4
46 21 Where X (µg) is the total amount of uranium in adsorbent at equilibrium, m (g) is the
47
48 22 dosage of adsorbent, C μg/L) is the concentration of uranium at equilibrium,
49
50 23 Q μg/g) is the adsorption capacity of uranium at equilibrium, Q= and b are
51
52 24 Langmuir constants related to adsorption capacity and adsorption energy, respectively.
53
54 25 The plot of C /Q against C is shown in Figure S3a.
55
56
57
58
59 14
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2
3 1 The Freundlich model is widely applied to describe the adsorption of uranium on
4
5 2 heterogeneous surfaces as well as multilayer adsorption and it is tested in the following
6
7 3 equation:
8
9 ⁄
4  = > ×  * ? (9)
10
11
12 5 A new linear equation can be derived from equation (9) as follows:
13 1
14 ln  = ln> + ln 10)
15
A
16 6 Where K B and n are the Freundlich constants related to adsorption capacity and
17
18 7 adsorption intensity, respectively. The plot of ln Q against ln C is shown in Figure
19
20 8 S3b.
21
22 9 The isotherm parameters of Q= , b, KF, n and the correlation coefficient R2 are
23
24
10 calculated accordingly and summarized in Table2. It can be seen that Langmuir model
25 11 (R2=0.999) fits the experimental data better than Freundlich model (R2=0.756) and the
26
27 12 maximum adsorption capacity is 35.37 mg/g. The fact that the Langmuir model fits
28
29 13 the experimental data very well may be due to homogenous distribution of active sites
30
31 14 on the adsorbent surface, since the Langmuir equation assumes that the surface is
32
33 15 homogeneous.45
34
35 16 Considering many experimental conditions to affect the maximum adsorption
36
37 17 capacity of adsorbents, such as pH, temperature, contact time and so on, it is difficult
38
39 18 to directly compare the adsorption capacities in reports in literature. Table 3 presents a
40
19 comparison of the maximum adsorption capacities for uranium ions of different
41
42 20 adsorbents. The maximum adsorption capacity of uranium on TMP-g-AO reaches
43
44 21 35.37 mg U/g at 298.15 K and pH 8.2±0.1, which is much higher than that on other
45
46 22 adsorbents except for AO-OMS under very similar experimental conditions.
47
48 23 Adsorbents such as UHMWPE, amidoxime-based polymeric, and nanofibrous
49
50 24 adsorbent, are investigated for the removal of uranium(VI), but all of them need more
51
52 25 time to arrive at equilibrium and their maximum adsorption capacities are lower than
53
54 26 that of TMP-g-AO. Although hematite can reach adsorption equilibrium in a shorter
55
56 27 time, its maximum adsorption capacity is less than one tenth of that of TMP-g-AO. As
57
58
59 15
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2
3 1 a result, the TMP-g-AO adsorbent is suitable for uranium(VI) extraction in weakly
4
5 2 alkaline solution or seawater.
6
7 3 3.2.5. Effect of Temperature and Thermodynamic Studies.The effect of temperature
8
9 4 on the adsorption of uranium(VI) was investigated at nine different temperatures of
10
11 5 288.15, 293.15, 298.15, 303.15, 308.15, 313.15, 318.15, 323.15 and 333.15 K. As
12
13 6 shown in Figure 11, the adsorption rate of uranium(VI) increases gradually as the
14
15 7 temperature increases. In other words, the higher temperature is beneficial to the
16
17 8 adsorption of uranium ions, which may be attributed to the fact that increasing
18
9 temperature can promote the movement of molecules.
19
20 10 The thermodynamic parameters of the adsorption process including Gibbs free
21
22 11 energy change (∆G), enthalpy change (∆H) and entropy change (∆S) can be calculated
23
24 12 using following equations.
25
26 ∆C = −DE FA G 11)
27
28 13 ∆C = ∆H − E∆I (12)
29
∆I ∆H
30 ln G = − 13)
31 D DE
32 14 Where K J is the equilibrium constant (Q /C ), T and R are the absolute temperature (K)
33
34
35 15 and the gas constant (8.314 J/mol/K), respectively. The plot of ln K J against 1/T is
36
37 16 shown in Figure S4, ∆S and ∆H can be obtained from the intercept and slope, and the
38
39 17 results are shown in Table 4.
40
18 The enthalpy change (∆H) and entropy change (∆S) of adsorption are 77.86 kJ/mol
41
42 19 and 295.73 J/mol/K. The positive value of ∆H demonstrates that the adsorption of
43
44 20 uranium(VI) ions is endothermic in nature, and the positive value of ∆S indicates the
45
46 21 stability of adsorption system and reflects an increase on the randomness during the
47
48 22 adsorption process. Furthermore, the value of ∆G decreases with increasing
49
50 23 temperature, which indicates that the adsorption process of uranium onto TMP-g-AO is
51
52 24 spontaneous and higher temperatures are feasible for uranium adsorption.
53
54 25 3.2.6. Desorption and Regeneration. Desorption and regeneration processes are very
55
56 26 important to evaluate the economic performance of absorbent in actual application. In
57
27 this study, the hydrochloric acid was used as desorption agent. The adsorption and
58
59 16
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2
3 1 desorption experiments were carried out five times. Table S4 show that both
4
5 2 adsorption and desorption rates slightly decline after five cycles. The declination of
6
7 3 adsorption rate may be attributed to the fact that the undesorbed uranium ions occupy
8
9 4 the binding sites due to insufficient contact time and the active sites of binding
10
11 5 uranium ions decrease on TMP-g-AO as the adsorption-desorption experiments
12
13 6 increase. It is reported that the sorption amount of uranium(VI) for AOGONRs
14
15 7 decreases slightly from 0.94 to 0.89 mmol/g after five consecutive sorption/desorption
16
17 8 cycles.46 Likewise, AO-HTC has a 7.37% decrement of sorption capacity after five
18
9 cycles.47 Although the adsorption rate of uranium on TMP-g-AO has a 1.42%
19
20 10 decrease after five cycles, it is less than that of AOGONRs and AO-HTC. As a result,
21
22 11 TMP-g-AO material has the potential of regeneration and reuse, which enhances the
23
24 12 economy of the adsorption process to some extent.
25
26 13 3.3. Application in Adsorption of Uranium from Seawater. From the experimental
27
28 14 results obtained, it can be seen that TMP-g-AO adsorbent has a high adsorption rate
29
30 15 and a large adsorption capacity for uranium ions in weakly alkaline solution and the
31
32 16 adsorption can reach equilibrium in a very short time. Furthermore, the adsorbent
33
34 17 exhibits a very good selectivity and affinity for uranium ions in the presence of
35
18 coexisting ions. In order to evaluate the potential application of TMP-g-AO for
36
37 19 uranium extraction from seawater, we carried out the experiments on adsorption of
38
39 20 uranium(VI) from natural seawater and the uranium-doped seawater. The natural
40
41 21 seawater used in the adsorption experiments came from near-surface seawater from
42
43 22 Hainan Province, China, collected in the tanks. The concentrations of uranium ions in
44
45 23 seawater and the uranium-doped seawater are 3.65 and 61.02 µg/L, respectively. After
46
47 24 three days of adsorption by the adsorbent (0.05 g) at 298.15 K, the concentrations
48
49 25 decreased to 0.66 and 1.34 µg/L, the adsorption rates of uranium(VI) reached to 81.92%
50
51
26 and 97.80%, respectively. This demonstrates that the material still has high adsorption
52
27 rate in high salinity and multi-ionic solutions. Therefore, TMP-g-AO has great
53
54 28 potential application in the area of separation and enrichment of uranium from
55
56 29 seawater.
57
58 30
59 17
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2
3
4 1 4.CONCLUSIONS
5
6 2 A novel TMP-g-AO adsorbent was developed for highly efficient extraction of
7
8 3 uranium from seawater. The TMP-g-AO adsorbent was synthesized by chemical
9
10 4 co-precipitation and subsequent chemical modifications. According to the batch
11
12 5 adsorption experiment, the adsorption rate and capacity are influenced by adsorbent
13
14 6 dosage, coexisting ions, initial uranium concentration, contact time and temperature to
15
16 7 some extent. In addition, the synthetic process and uranium adsorption were
17
8 characterized by SEM-EDS, FT-IR, XPS, N2-BET and Thermal analysis. SEM images
18
19 9 show that TMP-g-AO is spherical shape particle of nanoscale and the surfaces of the
20
21 10 samples become rough and dense during chemical modification processes. A sharp
22
23 11 peak at 2242 cm-1 indicates the successful grafting of acrylonitrile and new
24
25 12 characteristic peaks at 3194, 1649, 1269 and 920 cm-1 demonstrate the conversion of
26
27 13 nitrile group into the amidoxime group. The results of EDS, FT-IR and XPS show that
28
29 14 uranium ion is adsorbed on the surface of TMP-g-AO after adsorption. The values of
30
31 15 BET surface area, pore volume, and average pore diameter from N2-BET analysis are
32
33
16 48.183 m2/g, 0.116 cm3/g and 3.911 nm, respectively, which indicate that the pore
34
17 volume of TMP-g-AO is very small due to its dense surface. The results of TGA and
35
36 18 DTG analyses show that the mass ratio of the polymerized amidoxime group to
37
38 19 TMP-g and the weight percent of the polymerized amidoxime group in dry
39
40 20 TMP-g-AO are 0.423:1 and 29.7%, respectively.
41
42 21 The kinetic study suggests that uranium adsorption onto TMP-g-AO follows the
43
44 22 pseudo-second-order kinetic model. The adsorption equilibrium data fit the Langmuir
45
46 23 isotherm model well and the maximum adsorption capacity of uranium is 35.37 mg/g
47
48 24 at 298.15 K and pH 8.2±0.1. The results of thermodynamic study show that the
49
50
25 adsorption process is spontaneous and endothermic. The functional TMP-g-AO
51 26 adsorbent exhibits very good selectivity and affinity for uranium ions under
52
53 27 coexisting multi-metal ions except for Fe3+ and Co2+. Desorption is performed and the
54
55 28 adsorption rate of uranium on TMP-g-AO only has a 1.42% decrease after five
56
57 29 consecutive adsorption-desorption cycles. The TMP-g-AO adsorbent also has high
58
59 18
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1
2
3 1 adsorption rate for uranium in seawater. As a result, the TMP-g-AO could be a very
4
5 2 promising adsorbent for uranium extraction from seawater.
6
7 3
8
9
10 4 ACKNOWLEDGMENTS
11
12 5 This work was supported by the National Natural Science Foundation of China
13
14
15 6 (91326106, U1401321 and 114055081), the Development Program for Science and
16
17 7 Technology for National Defense (B3720132001) and the Research Foundation of
18
19
20 8 Education Bureau of Hunan Province (16C1386).
21
22 9
23
24 10 References:
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26 11 1. Zhang, X.; Wang, J.; Li, R.; Dai, Q.; Gao, R.; Liu, Q.; Zhang, M., Preparation of
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28 12 Fe3O4@ C@ layered double hydroxide composite for magnetic separation of uranium.
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30 13 Ind. Eng. Chem. Res. 2013, 52, 10152-10159.
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14 2. Kim, J.; Tsouris, C.; Oyola, Y.; Janke, C. J.; Mayes, R. T.; Dai, S.; Gill, G.; Kuo,
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35 16 Amidoxime-Based Polymeric Adsorbent: Field Experiments, Modeling, and Updated
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37 17 Economic Assessment. Ind. Eng. Chem. Res. 2014, 53, 6076-6083.
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39 18 3. Gunathilake, C.; Górka, J.; Dai, S.; Jaroniec, M., Amidoxime-modified
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41 19 mesoporous silica for uranium adsorption under seawater conditions. J. Mater. Chem.
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43 20 A. 2015, 3, 11650-11659.
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45 21 4. Kim, J.; Tsouris, C.; Mayes, R. T.; Oyola, Y.; Saito, T.; Janke, C. J.; Dai, S.;
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47 22 Schneider, E.; Sachde, D., Recovery of uranium from seawater: A review of current
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23 status and future research needs. Sep. Sci. Technol. 2013, 48, 367-387.
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52 25 calcium alginate beads. J. Hazard. Mater. 2009, 168, 369-375.
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54 26 6. Shao, D.; Hou, G.; Li, J.; Wen, T.; Ren, X.; Wang, X., PANI/GO as a super
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24 12 with phosphate group. J. Radioanal. Nucl. Chem. 2014, 300, 1235-1244.
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26 13 11. Sun, Y.; Ding, C.; Cheng, W.; Wang, X., Simultaneous adsorption and reduction
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32 16 12. Li, Z.; Chen, F.; Yuan, L.; Liu, Y.; Zhao, Y.; Chai, Z.; Shi, W., Uranium(VI)
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43 22 14. Zhang, H.; Xue, J. H.; Hu, N.; Sun, J.; Ding, D. X.; Wang, Y. D.; Li, L., Selective
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26 13 Chem. 2008, 390, 1927-32.
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49 25 24. Bayramoglu, G.; Arica, M. Y., MCM-41 silica particles grafted with
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27 uranium removal from aqueous medium. Micropor. Mesopor. Mat. 2015, 226,
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3 1 Figure captions
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5 2 Figure 1. SEM images (TMP (a), TMP-g (b), TMP-g-AN (c), TMP-g-AO (d) and
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3 TMP-g-AO-U (e)) and EDS (TMP-g-AO (f) and TMP-g-AO-U (g)).
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4 Figure 2. FT-IR of TMP (a), TMP-g (b), TMP-g-AN (c), TMP-g-AO (d) and
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10 5 TMP-g-AO-U (e).
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12 6 Figure 3. XPS full-scan spectra and U4f spectra of TMP-g-AO and TMP-g-AO-U.
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14 7 Figure 4. C1s and N1s spectra of TMP-g-AO and TMP-g-AO-U.
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16 8 Figure 5. Adsorption-desorption isotherms of nitrogen on TMP-g-AO.
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18 9 Figure 6. TGA and DTG analyses of TMP-g-AO.
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20 10 Figure 7. Effect of adsorbent dosage on adsorption rate and capacity of uranium(VI)
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22 11 (V=50 mL, C0=65 µg/L, pH=8.2±0.1, t=120 min, T=298.15 K).
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12 Figure 8. Comparison of selectivity and distribution coefficients of coexisting ions on
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13 TMP-g-AO (V=50 mL, pH=8.2±0.1, m=0.05 g, T=298.15 K).
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27 14 Figure 9. Effect of contact time on adsorption rate of uranium(VI) (V=100 mL,
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29 15 pH=8.2±0.1, m=0.1 g, T=298.15 K).
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31 16 Figure 10. Effect of initial uranium concentration on adsorption capacity of uranium(VI)
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33 17 (V=50 mL, pH=8.2±0.1, m=0.05 g, T=298.15 K).
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35 18 Figure11. Effect of temperature on adsorption rate of uranium(VI) (V=50 mL, C0=65
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37 19 µg/L, pH=8.2±0.1, t= 120 min, m=0.05 g).
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1 Table 1. Parameters for kinetic models of uranium(VI) adsorption onto
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5 2 TMP-g-AO
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7 Pseudo-first-order kinetics Pseudo-second-order kinetics
8 Concentration Q (exp)
9 Q (cal) Q (cal)
10 (µg/L) (µg/g) k1(min-1) R2 k2(min-1) R2
11 (µg/g) (µg/g)
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13 42.3 42.26 0.0318 8.53 0.833 0.0058 42.63 0.999
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15 104.8 104.47 0.0316 27.09 0.828 0.0018 105.71 0.999
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17 226.5 211.01 0.0265 85.88 0.990 0.0006 210.97 0.998
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1 Table 2. Constants for adsorption isotherm models for uranium(VI) adsorption
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7 Langmuir Freundlich
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9 Q= (103µg/g) b R2 KF n R2
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11 35.37 3.3 0.999 13.21 2.03 0.756
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3 1 Table 3. Comparison of adsorption capacities for uranium ion of various
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6 Experimental 4KL
7 Adsorbent Reference
8 conditions (mg/g)
9 42
10 UHMWPE 298.15±1K, pH8.1±0.3, 42 days 1.97
11 48
12 pA 296.15 K,pH8,72 hours 14.8
13 2
Amidoxime-based polymeric 293.15 K, seawater, 8 weeks 3.3
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ambient temperature, simulated
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17 seawater, 24 hours
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19 Hematite 293 K, pH7, 6 hours 3.36 56

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21 Nanofibrous adsorbent 298.15±2 K, pH8, 30 days 2.86
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23 TMP-g-AO 298.15 K, pH8.2±0.1, 72 hours 35.37 This work
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1 Table 4. Thermodynamic parameters for uranium(VI) adsorption onto
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5 2 TMP-g-AO.
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7 ∆H (kJ/mol) ∆S (J/mol·K) T(K) ∆G (kJ/mol) R2
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9 77.86 295.73 288.15 -7.35 0.953
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11 293.15 -8.83
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13 298.15 –10.31
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15 303.15 –11.79
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17 308.15 –13.27
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313.15 –14.75
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22 323.15 -17.71
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24 333.15 -20.66
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