Supporting Information. Exceptional Perrhenate/Pertechnetate Uptake and Subsequent. Immobilization by a Low-Dimensional Cationic Coordination

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1 Supporting Information Exceptional Perrhenate/Pertechnetate Uptake and Subsequent Immobilization by a LowDimensional Cationic Coordination Polymer: Overcoming the Hofmeister Bias Selectivity Lin Zhu,,, Chengliang Xiao,,, Xing Dai,, Jie Li,, Daxiang Gui,, Daopeng Sheng,, Lanhua Chen,, Ruhong Zhou,, Zhifang Chai,, Thomas E. AlbrechtSchmitt,,, Shuao Wang * School for Radiological and Interdisciplinary Sciences (RADX), Soochow University, , Suzhou, P. R. China Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, , Suzhou, P. R. China Department of Chemistry and Biochemistry, Florida State University, 95 Chieftain Way, Tallahassee, Florida 32306, United States These authors contribute equally * Corresponding authors. shuaowang@suda.edu.cn (SHUAO WANG); Tel: ; Fax: Number of page: 23; Number of Figures: 14 (Figure S1 to Figure S14); Number of Tables: 8 (Tables S1 to Table S8); 1

2 Table of Contents 1. Additional Details about Materials and Methods 2. Characterization Techniques 3. Single Crystal Structure Measurement 4. Anion Competition Studies 5. Thermodynamic Study 6. Figure S1. Crystallographic structure of [Ag4,4 bipyridine] + layers of a, b) SBN and c, d) SBR viewed in different axis 7. Hydrolytic Stability Measurements. 8. Figure S2. Powder Xray diffraction (PXRD) patterns of SBN samples after immersed in aqueous solution with different ph values ranging from 3 to Figure S3. Equations of (a) Langmuir model and (b) Freundlich model for SBN and Purolite A532E 10. Figure S4. Effect of different anions (~0.5mM) on the removal percentage of ReO4 by SBN 11. Figure S5. Optical microscope photograph of (A, B) SBN; (C) SBN/SBR after 5 min exposure to perrhenate solution; (D) SBR 12. Figure S6. SEM images of SBN (A,B)and SBR (C,D) 13. Figure S7. a) FTIR spectra of the original SBN and exchanged ReO4 sample. b) PXRD patterns of assynthesized (blue) SBN, ReO4 exchanged (pink) and simulated (black) SBR 14. Figure S8. Powder Xray diffraction (PXRD) patterns of SBN samples after immersed in different concentration of ReO4 solution with ReO4/ SBN mole ratio ranging from 0.25 to Figure S9. STEMEDS mapping profiles of ReO4 exchanged SBN 16. Figure S10. Effect of ph on solubility product constant of SBN (pink) and SBR (purple) and the instantaneous derivative of Gibb s energy for anion exchange of SBN (blue) 17. Figure S11. The dissolution concentration of Ag+ and ReO4 on SBR under 2

3 different ph 18. Figure S12. PXRD patterns of assynthesized (black) SBN, SBR (blue) and SBR after immerged into concentration of 0.5 and 1 mol/l NaNO3 aqueous solutions (olive and red) 19. Figure S13. Powder Xray diffraction (PXRD) patterns of SBR samples after immersed in different types of anions solution (~0.5 mm) 20. Figure S14. Thermogravimetric analysis of SBR 21. Table S1. Structural and thermodynamic comparison between ReO 4 TcO 4 and 22. The Sorption data Fitting by Isotherm Models 23. Table S2 Fitting results from the Langmuir and Freundlich fitting 24. Table S3. Comparison of sorption capacities of Re(VII) onto various sorbents 25. Table S4. Crystal data and structure refinements for SBR 26. Table S5. Hydrogen bonds distances (Å) and AgO bonds distances (Å) of compound SBN and SBR optimized by theoretical calculation 27. Table S6. Extent of anion exchange in water for [Ag(4,4 bipy)x] at Table S7. The solubility product of some perrhenate and pertechnetate salts 29. Table S8. The dissolution studies of SBR after immersed in different types of anions solution (~0.5 mm) at 25 3

4 Additional Details about Materials and Methods Synthesis of SBN: SBN material was synthesized by hydrothermal method. Typically, a mixture of AgNO 3 (0.1 g), 4,4 bipyridine (0.1 g), and deionized water (10 ml) was stirred at room temperature for 5 min and then loaded into a 20 ml Teflon lined autoclave. The autoclave was sealed and heated to 140 C for 10 h and then cooled to 110 C for 8 h, followed by further cooling to 90 C for 6 h and final cooling to room temperature at a rate of 0.1 C min 1. The product was rinsed with deionized water and acetone before being dried in air at room temperature. 1,2 Synthesis of NDTB1: Th(NO 3 ) 4 4H 2 O ( g, mmol), boric acid ( g, mmol), and deionized water (90 µl) were loaded into a 20 ml autoclave. The autoclave was sealed and heated to 200 C in a box furnace for 7 days. The autoclave was then cooled down to 160 C at a rate of 1 C h 1 and then cooled further to room temperature at a rate of 9 C h 1. The product was washed with boiling water to remove excess boric acid and subsequently rinsed with methanol. 3 Synthesis of MgAlLDH: To prepare LDH by conventional coprecipitation method, MgCl 2 6H 2 O and AlCl 3 9H 2 O with Mg 2+ : Al 3+ molar ratio of 2:1 were dissolved in 50 ml of deionized water and then a certain concentration of NaOH solution was added dropwise into the mixture solution with stirring to adjust the ph values to 10 under nitrogen purging to avoid, or at least minimize, the contamination by atmospheric CO 2. The resulting slurry was stirred overnight under a nitrogen flow at 70 C. The precipitate was subsequently centrifuged, washed thoroughly with deionized water, and dried at 80 C. 4 Synthesis of Yb 3 O(OH) 6 Cl 2H 2 O: Yb 3 O(OH) 6 Cl 2H 2 O was prepared via a hydrothermal synthesis. Typically, 7.5 ml of a 0.44 M aqueous solution of YbCl 3 nh 2 O was added to 2.5 ml of an aqueous solution containing 2.1 M NaOH and 1.44 M NaCl. A gelatinous precipitate was formed instantaneously and the resulting mixture was treated hydrothermally at 220 ºC for 14 h. The resulting product was then filtered, washed with deionized water and ethanol before being dried in air at room temperature. 5 4

5 Characterization Techniques Powder Xray diffraction (PXRD) data were collected from 5 to 50 o with a step of 0.02 o on a Bruker D8 Advance diffractometer with Cu Kα radiation (λ= Å) and a Lynxeye onedimensional detector. The FTIR was recorded in the range of cm 1 on a Thermo Nicolet is50 spectrometer. SEM images were recorded on a FEI Quanta 200FEG scanning electron microscope (SEM). TEM images were obtained by a Tecnai G2 spirit BioTwin transmission electron microscopy (TEM). Single Crystal Structure Measurement. Data collection was performed on a Bruker D8Venture diffractometer with a Turbo Xray Source (Mo Kα radiation, λ = Å) adopting the direct drive rotating anode technique and a CMOS detector at room temperature. The data frames were collected using the program APEX 2 and processed using the program SAINT routine in APEX 2. The structures were solved by direct methods and refined by the fullmatrix least squares on F 2 SHELXTL97 program. 6 using the Anion Competition Studies. The effect of NO 3 was performed by adding 0.15 mm, 0.75 mm, 1.5 mm, 3 mm, or 15 mm NaNO 3 solutions respectively into a 0.15 mm ReO 4 solution. The competing effect of other anions including CO 3 2, H 2 PO 4, SO 4 2, Cl and ClO 4 were initially performed by adding 0.5 mm Na 2 SO 4, Na 2 CO 3, or NaH 2 PO 4 solutions receptively into a 0.5 mm ReO 4 solution. The solid/liquid ratio performed in all experiments was 0.5 g/l. SBN solid was added in the above solution, respectively. The concentrations of ReO 4 after sorption in aqueous solution were determined by ICPOES. Thermodynamic study. In the case of anion exchange, the standard thermodynamic equilibrium constant K can be expressed as a ratio of solubility product constants K sp for the starting and resultant complex. K = [MLX ][X ][S] [MLX ][X ][S] = [MLX ][S] [MS ][X ][L] [MS ][X ][L] [MLX ][S] =K 5 K ( 1)

6 Where M are metal ions (Ag + ), L are ligands (4,4 bipyridine), X 1, X 2 are anions and S is solvent. The solubility product constants K and K are for SBN and SBR, respectively. The reaction quotient Q can be expressed as equation (S2) Q= [X ] [X ] ( 2) Therefore, the instantaneous derivative of Gibbs free energy for anion exchange ( G(T)) were calculated according to equation (S3), which is expressed as followed. G(T)= G(T) RTlnQ= RTln K RTln [X K [X ] ] ( 3) Equations (4) suggests that a larger value of K sp1 /K sp2 should lead to a higher percentage of conversion of SBN to SBR. 7 Figure S1. Crystallographic structure of [Ag4,4bipy] + layers of a, b) SBN and c, d) SBR viewed in different axis. Atom colors: Ag = orangered, N = blue, C = light blue. 6

7 Hydrolytic Stability Measurements. Hydrolytic stability measurements for SBN was studied by soaking the samples in HNO 3 or NaOH of different phs and the resulting mixture was stirred for conducted for 12 h. The PXRD results demonstrate that SBN is stable in aqueous solutions at phs ranging from 3 to 10. Intensity (a.u.) θ (degree) ph10 ph9 ph8 ph7 ph6 ph5 ph4 ph3 Experimental Simulated Figure S2. Powder Xray diffraction (PXRD) patterns of SBN samples after immersed in aqueous solution with different ph values ranging from 3 to 10. (a) c e /q e SBN SBN Langmuir model PuroliteA532E PuroliteA532E Langmuir model c e (mg L 1 ) (b) lnq e SBN SBN Freundlich model PuroliteA532E PuroliteA532E Freundlich model lnc e Figure S3. Equations of (a) Langmuir model and (b) Freundlich model for SBN and Purolite A532E. 7

8 Removal rate (%) Blank H 2 PO 4 SO 4 2 CO 3 2 NO 3 ClO 4 Cl 0 Figure S4. Effect of different anions (~0.5mM) on the removal percentage of ReO 4 by SBN. Figure S5. Optical microscope photograph of (A, B) SBN; (C) SBN/SBR after 5 min exposure to perrhenate solution; (D) SBR. 8

9 Figure S6. SEM images of SBN (A,B)and SBR (C,D). 9

10 Transmittance (a.u.) SBN SBNReO Wavenumber/cm 1 Intensity (a.u.) Simulated SBNReO 4 SBN SBNReO θ (degree) Figure S7. a) FTIR spectra of the original SBN and exchanged ReO 4 sample. b) PXRD patterns of assynthesized (blue) SBN, ReO 4 exchanged (pink) and simulated (black) SBR. 10

11 Intensity (a.u.) SBR 1:1 1:0.5 1:0.25 SBN θ (degree) Figure S8. Powder Xray diffraction (PXRD) patterns of SBN samples after immersed in different concentration of ReO 4 solution with ReO 4 / SBN mole ratio ranging from 0.25 to 1. Figure S9. STEMEDS mapping profiles of ReO 4 exchanged SBN. 11

12 SBN SBR K sp G (KJ) ph Figure S10. Effect of ph on solubility product constant of SBN (pink) and SBR (purple) and the instantaneous derivative of Gibb s energy for anion exchange of SBN (blue) Ag + release (mmol /L) SBRAg SBRRe release (mmol /L) ReO ph 0.0 Figure S11. The dissolution concentration of Ag + and ReO 4 on SBR under different ph. 12

13 Intensity (a.u.) 1M NaNO 3 0.5M NaNO 3 SBNRe SBN θ (degree) Figure S12. PXRD patterns of assynthesized (black) SBN, SBR (blue) and SBR after immerged into concentration of 0.5 and 1 mol/l NaNO 3 aqueous solutions (olive and red). Intensity (a.u.) SBR CO 3 2 SBR H 2 PO 4 SBR θ (degree) Figure S13. Powder Xray diffraction (PXRD) patterns of SBR samples after immersed in different types of anions solution (~0.5 mm). 13

14 100 SBR Weight(%) Temperature Figure S14. Thermogravimetric analysis of SBR. Table S1. Structural and thermodynamic comparison between ReO 4 and TcO 4. 8 ReO 4 TcO 4 pk a Charge/volume (1/ Å 3 ) DG hydr (kj mol 1 ) UVVis bands (nm) , 280 r(xo/ Å) (X=Re, Tc) R a H2O (Å) Q/S 10 2b (Å 2 ) R H2O = ionic radius in water. Q/S = surface charge density of an ion. Sorption data Fitting by Isotherm Models The Langmuir model assumes that the sorption of metal ions occurs on a homogenous surface by monolayer sorption and there no interaction between adsorbed ions, with homogeneous binding sites and equivalent sorption energies. The linear equation of the Langmuir isotherm model is expressed as followed 9 : ce 1 c = + q q k q e m L m where q m is the maximum sorption capacity corresponding to complete monolayer 14 e

15 coverage (mg/g) and k L is a constant indirectly related to sorption capacity and energy of sorption (L/mg), which characterizes the affinity of the adsorbate with the adsorbent. The linearized plot was obtained when we plotted C e /q e against C e and q m and k L could be calculated from the slope and intercept. The Freundlich equation is an empirical equation based on sorption on a heterogeneous surface. The isotherm assumes that adsorbent surface sites have a spectrum of different binding energies. The linear equation can be expressed by: 1 ln q = ln k + ln c n e F e where k F and n are the Freundlich constants related to the sorption capacity and the sorption intensity, respectively. The linear plot was obtained by plotting lnq e against lnc e, and the values of k F and n were calculated from the slope and intercept of the straight line. Table S3 shows the fit results from the Langmuir and Freundlich equations. Table S2. Fitting results from the Langmuir and Freundlich fitting. Langmuir Freundlich q m (mg g 1 ) K L (L mg 1 ) R 2 k F (L n /mol n1 g) n R 2 LDHs NDTB Yb 3 O(OH) 6 Cl PuroliteA532E > SBN >

16 Table S3. Comparison of sorption capacities of Re(VII) onto various sorbents. Sorbents Experimental conditions Adsorption capacity (mg/g) reference PSg4VPIE Ambient temperature; 2h 252 Biochar T=298K; 12h; 3g/L PolyDMAEMA hydrogels ph2; I= Blown algae Ambient temperature; ph NanoSiO 2 T=298K; ph UiO66NH 3 + Molar ratio ReO 4 : UiO66NH 3 + =1:2; 24h Acidosasa edulis shoot shell biochar T=298K; 8h; ph1; 3g/L PAF1F Molar ratio ReO 4 : PAF1F =1:2; 24h D318 resin T=298K; ph5.2; 1g/L 351 PPg2VP ph2.2; appropriate temperature Ionimprinted microsphere T=298.15K; 8h; ph6; 0.1g/L R 2 SO 4 resin Ambient temperature; 1.3g/L; ph6.25; 4h ATR resin T=298K; 8h; ph2.6; 10h SLUG21 Ambient temperature; 1.6g/L; 48h SCU100 Ambient temperature; ph=7.0±0.1; 1g/L LDHs Ambient temperature; ph=7.0±0.1; 0.5g/L 130 Present work NDTB Ambient temperature; 49.4 Present 16

17 ph=7.0±0.1; 0.5g/L work Yb 3 O(OH) 3 Cl Ambient temperature; ph=7.0±0.1; 0.5g/L 48.6 Present work PuroliteA532E Ambient temperature; ph=7.0±0.1; 0.5g/L 446 Present work SBN Ambient temperature; ph=7.0±0.1; 0.5g/L 786 Present work 17

18 Table S4. Crystal data and structure refinements for SBR. SBR Empirical formula C 10 H 8 AgN 2 O 4 Re Formula weight Crystal system Space group Orthorhombic Pbca a(å) (3) b(å) (3) c(å) (3) α( ) 90 β( ) 90 γ( ) 90 Volume(Å 3 ) (9) Z 8 ρcalcd (g cm 3 ) µ(mm 1 ) F(000) 1888 R int Data collected 8098 Independent data 2564 Goodnessoffit R a 1 (I>2σ(I)) wr b 2 (I>2σ(I)) a R 1 = Σ F o F c /Σ F o. b wr 2 = Σw( F o 2 F c 2 ) /Σ w(f o ) 2 1/2, where w = 1/[σ 2 (F 2 o ) + (ap) 2 + bp]. P= (F 2 o + 2F 2 c )/3. 18

19 Table S5. Hydrogen bonds distances (Å) and AgO bonds distances (Å) of compound SBN and SBR optimized by theoretical calculation. Bond type Distance (Å) O1H SBN O2H O3H O1Ag O2Ag O3Ag O1H SBR O2H O3H O4H O1Ag O2Ag O3Ag O4Ag The distances of O4 to surrounding Ag + are longer than 5 Å, which means there is no metal coordination to O4. 19

20 Table S6. Extent of anion exchange in water for [Ag(4,4 bipy)x] at 25. Anion exchange [Ag(4,4 bipy)x] From NO to ReO4 3 at different ph Solubility of starting complex (S ) 1 [mmol L 1 ] Solubility of target complex (S 2 ) [mmol L 1 ] S 1 /S 2 K sp1 /K sp2 r G(T)/kJ ph ph ph ph ph ph ph ph ph Table S7. The solubility product of some perrhenate and pertechnetate salts. Precipitation agent Experimental Conditions K sp value Ref. 1,2,4,6Tetraphenylpyridinium acetatereo 4 1M NH ; TPPyTcO 4 ph Pr 4 NTcO ,23 NitronHReO ,24 AgReO TlReO ,25 CsReO KReO SBR 20, ph Present work 20

21 Table S8. The dissolution studies of SBR after immersed in different types of anions solution (~0.5 mm) at 25. Different types of Anions Solution Solubility of SBR [mmol L 1 ] BlankH 2 O H 2 PO 4 CO

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