Acetylcysteine-Functionalized Microporous Conjugated Polymers for. Potential Separation of Uranium from Radioactive Effluents

Transcription

1 Elctronic Supplmntary Matrial (ESI) for Journal of Matrials Chmistry A. This journal is Th Royal Socity of Chmistry 2017 Supporting Information Actylcystin-Functionalizd Microporous Conjugatd Polymrs for Potntial Sparation of Uranium from Radioactiv Efflunts Xiaoli Han, Miyun Xu, Sn Yang, Jun Qian, Daobn Hua a School for Radiological and Intrdisciplinary Scincs (RAD X) & Collg of Chmistry, Chmical Enginring and Matrials Scinc, Soochow Univrsity, Suzhou , China b Collaborativ Innovation Cntr of Radiological Mdicin of Jiangsu Highr Education Institutions, Suzhou , China Tabl of contnts Charactrization mthods...s2 Sorption kintics...s2 Sorption isothrms...s3 Distribution ratio (K d )...S3 Tabl S1...S4 Tabl S2...S5 Tabl S3...S5 Tabl S4...S6 Tabl S5...S6 Fig. S1...S7 Fig. S2...S7 Fig. S3...S8 Fig. S4...S8 Fig. S5...S9 Fig. S6...S9 Fig. S7...S10 Fig. S8...S10 Fig. S9...S11 Rfrncs...S11 S1

2 1. Charactrization mthods Infrard absorption spctra wr acquird by a Varian-1000 Fourir transform infrard (FT-IR) spctromtr. Solid-stat 13 C CP/MAS NMR masurmnts wr carrid out on a Brukr Avanc III modl 400 MHz NMR spctromtr at a MAS rat of 5 khz. Elmntal analysis (EA) was dtrmind by ELEMENTAR CHNOS Elmntal Analyzr. Th uranyl ions concntration was dtrmind by thrmo high rsolution inductivly coupld plasma mass spctromtr (ICP-MS, Elmnt II). Surfac aras and por siz distributions wr masurd by nitrogn sorption and dsorption at 77.3 K using th ASAP 2020 volumtric sorption analyzr. BET surfac aras wr calculatd ovr th rlativ prssur rang P/P 0. Sampls wr dgassd at 100 C for 10 h undr high vacuum bfor analysis. 60 Co gamma-ray irradiation was carrid out at 60 Co radiation laboratory of Soochow Univrsity. Th dos rat was 15 Gy/min. Malvrn Zta sizr (632.8 nm, H- N lasr) was usd to rcord th zta potntial and Z-avrag siz distribution of th corrsponding matrials. 2. Sorption kintics Psudo-first-ordr quation is dscribd as followd (1): k1 log( q qt ) logq ( ) t (1) whr q and q t (mg/g) ar th sorption capacity of U(VI) at quilibrium tim and contact tim t (min), rspctivly, and k 1 (min 1 ) rprsnts th psudo first ordr kintic constant. q and k 1 can b calculatd from th slop and intrcpt of th plot of log (q -q t ) vrsus t, rspctivly (Fig. S7A). Psudo-scond-ordr modl is xprssd as th following Equation (2): t q t k 2 1 q 2 t q (2) whr k 2 (g/mg/min) rprsnts th rat constant of th psudo-scond ordr modl, and can b dtrmind from th plot of t/q t against t (Fig. S7B). 3. Sorption isothrms Langmuir modl can b dscribd as Equation (3): S2

3 C 1 C q q b q max max (3) whr b (L/mg) is th Langmuir constant rlatd to th affinity of binding sits, and q max (mg/g) is th maximum sorption capacity. Thy can b calculatd from th linar plot of C /q against C (Fig. S8A and S9A). Th Frundlich modl 1 is applid for multilayr sorption, which can b dscribd as Equation (4): logq log K F 1 logc n (4) whr K F [mg/g (L/mg) 1/n ] and n ar th Frundlich constants rlatd to sorption capacity and sorption intnsity, rspctivly, which can b calculatd from th linar plot of log q vrsus log C (Fig. S8B and S9B). 4. Distribution ratio (K d ) Th distribution ratio (K d ) is calculatd according to Equation (5): K d C0 C C V M (5) whr C 0 and C (mg/l) ar th initial and quilibrium concntration of uranyl ions, rspctivly. M (g) is th wight of sorbnt, and V (L) is th volum of th tsting solution. S3

4 Tabl S1. Comparison of sorption rat and sorption capacity of U(VI) on various uranium sorbnts. Sorbnts Exprimntal conditions Sorption quilibration tim Sorption capacity (mg/g) Rfrncs F 3 O 2 -AO ph 5.0, T 298 K 4h Amino functional MOFs ph 5.5, T 298 K 50min Poly(acrylic acid)- functionalizd microsphrs ph 4.5, T 298 K 2.5h GO-ACF ph 5.5, T 298 K 1h SBA-15 ph 4.0, T 298 K 3h 65 5 Msoporous carbon ph 4.0, T 298 K 5min 67 6 MA-TMA ph 4.5, T 298 K 10min Bnzimidazol-functionalizd 2D COF ph 4.5, T 298 K 30min MCP-3 ph 5.5, T 298 K 40s 165 This work S4

5 Tabl S2. Kintic paramtrs for th sorption of U(VI) by MCP-1,2,3,4. (Exprimntal condition: 1 mg of sorbnt dos, 5 ml of solution, mol/l U(VI), ph 5.5 ± 0.1, and K.) Psudo-first ordr Psudo-scond ordr Matrial q,xp (mg/g) k 1 (/min) q,cal (mg/g) R 2 k 2 (g/mg/min) q,cal (mg/g) R 2 MCP MCP MCP MCP Tabl S3. Langmuir and Frundlich paramtrs for U(VI) sorption by th MCPs. (Exprimntal conditions: 1 mg of sorbnt dos, 5 ml of solution, mol/l ~ mol/l U(VI), ph 5.5 ± 0.1, and K, contact tim = 20 min) Langmuir Frundlich Matrial q max (mg/g) b (L/mg) R 2 K F (L/g) n R 2 MCP MCP MCP MCP S5

6 Tabl S4. Langmuir and Frundlich paramtrs for U(VI) sorption by th MCPs. (Exprimntal conditions: 1 mg of sorbnt dos, 5 ml of solution, mol/l ~ mol/l U(VI), ph 5.5 ± 0.1, and K, contact tim = 20 min.) Matrial Langmuir Frundlich q max (mg/g) b (L/mg) R 2 K F (L/g) n R 2 MCP MCP MCP MCP Tabl S5. Comparison of th diamtr of coxisting ions in th solution. * Spcis (UO 2 ) 3 (OH) + 5 (UO 2 ) 4 (OH) + 7 OH - NO - 3 Cr 3+ Co 2+ Ni 2+ Cd 2+ Nd 3+ Zn 2+ Siz (nm) *: Th data for mtal ions was from Priodic Tabl of Chmical Elmnts. Anions and uranyl complxs wr simulatd by Chm 3D softwar and CrystalMakr Dmo (Fig. S6 ), rspctivly. S6

7 Fig. S1 Disprsibility of MCP-0 (A) and MCP-1 (B) in watr. Fig. S2 (A) Nitrogn sorption (th bottom lin) /dsorption (th abov lin) isothrms and (B) por siz distribution for MCP-0, 1, 2, 3, 4. S7

8 Fig. S3 Distribution of U(VI) spcis in aquous solution ([U] = 0.67mmol/L and ph valus ranging from 1 to 7), which was simulatd by Mdusa program. Fig. S4 Zta potntial of MCP-1. S8

9 Fig. S5 Sorption isothrms of U(VI) on MCPs. (Exprimntal condition: 1 mg of sorbnt dos, 5 ml of solution, mol/l ~ mol/l U(VI), ph 5.5 ± 0.1, and K.) Fig. S6 Th diamtr of th uranium spcis by CrystalMakr Dmo. S9

10 Fig. S7 (A) Psudo-first ordr kintics and (B) psudo-scond ordr kintics for th sorption of U(VI) onto th MCPs. Fig. S8 (A) Langmuir sorption isothrm plots and (B) Frundlich sorption isothrm plots for th sorption of U(VI) onto th MCPs. S10

11 Fig. S9 (A) Langmuir sorption isothrm plots and (B) Frundlich sorption isothrm plots for th sorption of U(VI) onto th MCPs. (Exprimntal condition: 1 mg of sorbnt dos, 5 ml of solution, mol/l ~ mol/l U(VI), ph 5.5 ± 0.1, and K.) Rfrncs 1. Y. G. Zhao, J. X. Li, L. P. Zhao, S. W. Zhang, Y. S. Huang, X. L. Wu and X. K. Wang, Chmical Enginring Journal, 2014, 235, Z. Q. Bai, L. Y. Yuan, L. Zhu, Z. R. Liu, S. Q. Chu, L. R. Zhng, J. Zhang, Z. F. Chai and W. Q. Shi, Journal of Matrials Chmistry A, 2015, 3, S. Zhang, X. W. Shu, Y. Zhou, L. Huang and D. B. Hua, Chmical Enginring Journal, 2014, 253, Y. Wang, Z. S. Wang, Z. X. Gu, J. J. Yang, J. L. Liao, Y. Y. Yang, N. Liu and J. Tang, Journal of Radioanalytical and Nuclar Chmistry, 2015, 304, Y. L. Wang, L. J. Song, L. Zhu, B. L. Guo, S. W. Chn and W. S. Wu, Dalton Transactions, 2014, 43, M. Carboni, C. W. Abny, K. M. L. Taylor-Pashow, J. L. Vivro-Escoto and W. B. Lin, Industrial & Enginring Chmistry Rsarch, 2013, 52, B. Li, C. Y. Bai, S. Zhang, X. S. Zhao, Y. Li, L. Wang, K. Ding, X. Shu, S. J. Li and L. J. Ma, Journal of Matrials Chmistry A, 2015, 3, J. Li, X. D. Yang, C. Y. Bai, Y. Tian, B. Li, S. Zhang, X. Y. Yang, S. D. Ding, C. Q. Xia, X. Y. Tan, L. J. Ma and S. J. Li, Journal of Colloid and Intrfac Scinc, 2015, 437, S11