Supporting Information for manuscript entitled. Recovery of lithium from waste water using development of Li ion-imprinted. John Crittenden d *

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1 Supporting Information for manuscript entitled Recovery of lithium from waste water using development of Li ion-imprinted polymers Xubiao Luo a, Bin Guo a, Jinming Luo b, Siyu Zhang c, Shenglian Luo a *, John rittenden d * a Key Laboratory of Jiangxi Province for Persistent Pollutants ontrol and Resources Recycle, Nanchang Hangkong University, Nanchang , PR hina bkey Laboratory of Drinking Water Science and Technology, Research enter for Ec o-environmental Sciences, hinese Academy of Sciences, Beijing , People s Republic of hina c State Key Lab of Urban and Regional Ecology, Research enter for Eco-Environmental Sciences, hinese Academy of Sciences,Beijing , People s Republic of hina d School of ivil and Environmental Engineering, Georgia Institute of Technology, 828 West Peachtree Street, Atlanta, Georgia, 30332, United States This Supporting Information ontains the Following Sections: S1. hemicals used in this study S2. haracterization methods S3. Preparation of MH-Fe 3 O 2 S4. The mathematical derivation process of the mass flow rate equation Fig. S1 SEM photographs of (a) Fe 3 O 4, (b)fe 3 O 2 and (c) Fe 3 O Fig. S2 XRD patterns for (a) Fe 3 O 4, (b)fe 3 O 2 and (c) Fe 3 O Fig. S3 Effect of ph on adsorption capacity of Fe 3 O and Fe 3 O onditions: 50 mg sorbent, 50 ml of Li(I), concentration 10 mmol/l, shaking time 10 h, temperature Fig.S4 Langmuir isotherm for adsorption of Li + ion on Fe 3 O and Fe 3 O Fig. S5 Linear plot of t/qt vs. t for Fe 3 O and Fe 3 O Fig.S6 Regeneration cycles of Fe 3 O 2 IIP, onditions: sorbents 200 mg, concentration 10 mmol/l S1

2 Fig. S7 the ph (ph=1,3,6) effect on adsorption capacity. Table S1 Basic properties of the real waste water sampled from Dingxin o., Ltd in Shangrao city. Table S2 omparison of Fe 3 O with other adsorbents applied for the adsorption of Li + ions. In total, there are seven figures, two table, and the document length is seventeen pages. S2

3 S1. hemicals used in this study Lithium chloride monohydrate (Lil H 2 O), potassium chloride (Kl), sodium chloride (Nal), zinc nitrate hexahydrate (Zn(NO 3 ) 2 6H 2 O), copper nitrate trihydrate (u(no 3 ) 2 3H 2 O) and ethyleneglycol dimethacrylate (EGDMA) were supplied by Xilong hemical o., Ltd. (Guangdong, hina). N,N-dimethyl formamide (DMF) were obtained from Shanghai DeNuo hemical o., Ltd (Shanghai, hina). 2-methylol-12-crown-4 (2M124), allyl bromide and 3-(Trimethoxysilyl)propyl methacrylate (MATES) were purchased from Heowns o., Ltd. (Tianjin, hina).potassiumhydride and 2,2-azobisisobutyronitrile (AIBN) were bought from Aladdin hemistry o., Ltd (Shanghai, hina). Water was purified through a Milli-Q water system (Bedford, USA). All other chemicals were of analytical reagent grade. S3

4 S2. haracterization methods Infrared (IR) spectroscopy measurements were recorded with a Bruker (Ettlingen, Germany) ertex 70 FTIR spectrophotometer. A onteaa 700 (Analytik Jena, Germany) flame atom absorption spectrophotometry (FAAS) was used for determination of Li(I) ions. A WF-4000 microwave synthesizer was used for heating (Preekem Shanghai, hina). Nuclear magnetic resonance (NMR) spectra were recorded on a Bruker A-400 spectrometer in DMSO-d6. 1 HNMR chemical shifts (δ) in ppm were reported in down field from tetramethylsilane. The morphologies of Fe 3 O 4, Fe 3 O 2, and Fe 3 O 2 -IIP were observed using scanning electron microscope (SEM, Japan, Shimadzu). X-ray powder diffraction (XRD) was obtained on an automatic X-ray diffractometer (Rigaku D/max 2200P, Japan) with a u Kα radiation source. S4

5 S3. Preparation of MH-Fe 3 O 2 The Fe 3 O 4 magnetic nanoparticles were prepared according to Ref. [1]. Fe 3 O 2 microspheres were prepared according to Reference [2] with minor modication. Typically, magetite nanoparticles (5.00 g) and a mixture of 2-propyl alcohol and highly purified water (12/1 v/v, 260 ml) were added into a three-neck round-bottom flask (500 ml). Solution was evenly dispersed after sonication for 15 min at room temperature, to which ammonia solution (20 ml), and TEOS (33.3 ml) were added successively. After reaction at room temperature for under a continuous stirring12 h,the resultant product was collected by an external magnet, and rinsed with highly purified water for five times thoroughly. To modify the Fe 3 O 2 with a double bond, MATES (4 ml) was dropwise added into the mixture solvents of ethanol and water (1:1, v/v, 200 ml) containing dispersed Fe 3 O 2 nanoparticles (5.0 g) and the reaction was kept for 12 h at 40 0 under N 2 gas. Then the product was separated and washed by ethanol for several times, and dried in vacuum. S5

6 S4. The mathematical derivation process of the mass flow rate equation Mathematically, the mass flow rate of Li + ion is given by the expression: d = k f a ( s) (1) dt where k f is the mass transfer coefficient (m/s), a is the specific area available for mass transfer per unit volume of the contactor (7220 m 2 /m 3 ), is the concentration of Li + ion in bulk solution (mmol/l), s is the concentration of Li + ion at interface (mmol/l). Assume the adsorption fit linear isotherm, Q Q k + k m l s = (2) 1 l s where k is the adsorption equilibrium coefficient (L/mmol) and q is the adsorption capacity (mmol/g), which can be calculated by the following equation: Q= ( 0 s ) (3) M where is the contactor volume (0.2 L), M is the mass of Fe 3 O (0.1 g), and 0 is the initial concentration of Li + ion in bulk solution ( mmol/l). The specific area available for mass transfer per unit volume of the contactor can be obtained by eq (4): a S ' = p (4) ' where ' S is the surface area of single Fe 3 O (m 2 ), ' is the volume of single Fe 3 O (m 3 ), and p is the volume of total Fe 3 O ( nm 3 ). ombining Eqs. 1-4 yields: S6

7 S7 )] 1 4 ) 1 ( ( [ l m l l m p f k M Q k k M Q r k dt d = (5) where r is the radius of Fe 3 O (300 nm). To describe the sorption data with the model, we derived the concentration of Li + ion in bulk solution () as a function of time (t) with Eq. (5): b ht b + = 0 ] exp[ In eq 6, h and b are the fitting parameters. r k h p f 3 = and ) 1 4 ) 1 ( ( l m l l m k M Q k k M Q b =. Thus eq 6 is used to fit the experimental results with h and b as fitting parameters.

8 Fig. S1 SEM photographs of (a) Fe3O4, and (c) S8

9 Fig. S2 XRD patterns for (a) Fe 3 O 4, (b)fe 3 O 2 and (c) Fe 3 O S9

10 Fig. S3 Effect of ph on adsorption capacity of Fe 3 O onditions: 50 mg sorbent, 50 ml of Li(I), concentration 10 mmol/l, shaking time 10 h, temperature S10

11 Fig.S4 Langmuir isotherm for adsorption of Li + ion on Fe 3 O and Fe 3 O S11

12 Fig. S5 Linear plot of t/qt vs. t for Fe 3 O and Fe 3 O S12

13 Fig. S6 Regeneration cycles of Fe 3 O onditions: sorbents 200 mg, concentration 10 mmol/l. S13

14 Fig. S7 the ph (ph=0.3,3,6) effect on adsorption capacity. S14

15 Table S1 Basic properties of the real waste water sampled from Dingxin o., Ltd in Shangrao city. TO Li K Zn o r u Al Ni Pb d ph mg/g mm mm mm mm mm mm mm mm mm mm S15

16 Table S2 omparison of Fe 3 O with other adsorbents applied for the adsorption of Li + ions. Adsorbent Selectivity Magnetic Adsorption Ref. capacity (mg/g) Pitch binded network high no Agar gelated sphere high no Mn 2 O 3 no no a alginate beads no no Fe 3 O 2 -IIP high yes 4.1 This study S16

17 REFERENES [1] Wang, X. B.; Ding, X. B.; Zheng, Z. H.; Hu, X. H.; heng, X.; Peng,Y. X. Magnetic molecularly imprinted polymerparticles synthesized by suspension polymerization in silicone oil. Macromol. Rapid. omm. 2006, 27, [2] Wang, X.; Wang, L. Y.; He, X. W.; Zhang, Y. K.; Zhang, L. X. A molecularly imprinted polymer-coated nanocomposite of magnetic nanoparticles for estrone recognition. Talanta. 2009, 78, S17