1. Department of Chemical and Biomolecular Engineering (BK21 Four), Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea 2. Center for Nanomaterials and Chemical Reactions, Institute for Basic Science (IBS), Daejeon 34141, Republic of Korea
NaA zeolite (Si/Al = 1.00) has been commercially applied for capturing radioactive 90Sr2+ because of its high surface charge density, effectively stabilizing the multivalent cation. However, owing to its narrow micropore opening (4.0 Å), large micron-sized crystallites, and bulkiness of hydrated Sr2+, the Sr2+ exchange over NaA has been limited by very slow kinetics. In this study, we synthesized nanocrystalline low-silica X by minimizing a water content in a synthesis gel and utilizing a methyl cellulose hydrogel as a crystal growth inhibitor. The resulting zeolite exhibited high crystallinity and Al-rich framework (Si/Al of approximately 1.00) with the sole presence of tetrahedral Al sites, which are capable of high Sr2+ uptake and ion selectivity. Meanwhile, the zeolite with a FAU topology has a much larger micropore opening size (7.4 Å) and a much smaller crystallite size (~340 nm) than NaA, which enable significantly enhanced ion-exchange kinetics. Compared to conventional NaA, the nanocrystalline low-silica X exhibited remarkably increased Sr2+-exchange kinetics (> 18-fold larger rate constant) in batch experiments. Although both the nanocrystalline low-silica X and NaA exhibited comparable Sr2+ capacities under equilibrated conditions, the former demonstrated a 5.5-fold larger breakthrough volume than NaA under dynamic conditions, attributed to its significantly faster Sr2+-exchange kinetics.
. [J]. Frontiers of Chemical Science and Engineering, 2024, 18(9): 98.
Hyungmin Jeon, Susung Lee, Jeong-Chul Kim, Minkee Choi. Nanocrystalline low-silica X zeolite as an efficient ion-exchanger enabling fast radioactive strontium capture. Front. Chem. Sci. Eng., 2024, 18(9): 98.
Z Zhang , M Cheng , X Xiao , K Bi , T Song , K Q Hu , Y Dai , L Zhou , C Liu , X Ji . et al.. Machine-learning-guided identification of coordination polymer ligands for crystallizing separation of Cs/Sr. ACS Applied Materials & Interfaces, 2022, 14(29): 33076–33084 https://doi.org/10.1021/acsami.2c05272
2
D Delacroix , J P Guerre , P Leblanc , C Hickman . Radionuclide and radiation protection data handbook 2002. Radiation Protection Dosimetry, 2022, 98(1): 1–168 https://doi.org/10.1093/oxfordjournals.rpd.a006705
3
S V Avery . Caesium accumulation by microorganisms: uptake mechanism, cation competition, compartmentalization and toxicity. Journal of Industrial Microbiology, 1995, 14(2): 76–84 https://doi.org/10.1007/BF01569888
4
D K GuptaC Walther. Behaviour of strontium in plants and the environment. 2018, Springer, Cham
5
K M A El-Rahman , A M El-Kamash , M R El-Sourougy , N M Abdel-Moniem . Thermodynamic modeling for the removal of Cs+, Sr2+, Ca2+ and Mg2+ ions from aqueous waste solutions using zeolite A. Journal of Radioanalytical and Nuclear Chemistry, 2006, 268(2): 221–230 https://doi.org/10.1007/s10967-006-0157-y
6
E Han , Y G Kim , H M Yang , I H Yoon , M Choi . Synergy between zeolite framework and encapsulated sulfur for enhanced ion-exchange selectivity to radioactive cesium. Chemistry of Materials, 2018, 30(16): 5777–5785 https://doi.org/10.1021/acs.chemmater.8b02782
7
S Kwon , C Kim , E Han , H Lee , H S Cho , M Choi . Relationship between zeolite structure and capture capability for radioactive cesium and strontium. Journal of Hazardous Materials, 2021, 408: 124419 https://doi.org/10.1016/j.jhazmat.2020.124419
8
X Zhang , Y Liu . Ultrafast removal of radioactive strontium ions from contaminated water by nanostructured layered sodium vanadosilicate with high adsorption capacity and selectivity. Journal of Hazardous Materials, 2020, 398: 122907 https://doi.org/10.1016/j.jhazmat.2020.122907
9
H Zhang , C Li , X Chen , H Fu , Y Chen , S Ning , T Fujita , Y Wei , X Wang . Layered ammonium vanadate nanobelt as efficient adsorbents for removal of Sr2+ and Cs+ from contaminated water. Journal of Colloid and Interface Science, 2022, 615: 110–123 https://doi.org/10.1016/j.jcis.2022.01.164
10
R G Anthony , C V Philip , R G Dosch . Selective adsorption and ion exchange of metal cations and anions with silico-titanates and layered titanates. Waste Management, 1993, 13(5–7): 503–512 https://doi.org/10.1016/0956-053X(93)90080-G
11
S Chitra , S Viswanathan , S V S Rao , P K Sinha . Uptake of cesium and strontium by crystalline silicotitanates from radioactive wastes. Journal of Radioanalytical and Nuclear Chemistry, 2011, 287(3): 955–960 https://doi.org/10.1007/s10967-010-0867-z
12
S Wang , S Ning , W Zhang , S Zhang , J Zhou , X Wang , Y Wei . Synthesis of carboxyl group functionalized silica composite resin for strontium removal. Materials & Design, 2020, 185: 108224 https://doi.org/10.1016/j.matdes.2019.108224
13
M J Manos , N Ding , M G Kanatzidis . Layered metal sulfides: exceptionally selective agents for radioactive strontium removal. Proceedings of the National Academy of Sciences of the United States of America, 2008, 105(10): 3696–3699 https://doi.org/10.1073/pnas.0711528105
14
S Schneider , A C Garcez , M Tremblay , F Bilodeau , D Lariviere , F Kleitz . Nanoporous ammonium molybdophosphate-silica hybrids as regenerable ultra-selective extraction agents for radiocesium monitoring. New Journal of Chemistry, 2013, 37(12): 3877–3880 https://doi.org/10.1039/c3nj01236k
15
H Jeon , J Seok , Y Ha , J C Kim , H S Cho , H M Yang , M Choi . First successful synthesis of an Al-rich mesoporous aluminosilicate for fast radioactive strontium capture. Journal of Hazardous Materials, 2023, 451: 131136 https://doi.org/10.1016/j.jhazmat.2023.131136
16
J Zhang , L Chen , D Gui , H Zhang , D Zhang , W Liu , G Huang , J Diwu , Z Chai , S Wang . et al.. An ingenious one-dimensional zirconium phosphonate with efficient strontium exchange capability and moderate proton conductivity. Dalton Transactions, 2018, 47(15): 5161–5165 https://doi.org/10.1039/C8DT00508G
17
J Zhang , L Chen , X Dai , L Chen , F Zhai , W Yu , S Guo , L Yang , L Chen , Y Zhang . et al.. Efficient Sr-90 removal from highly alkaline solution by an ultrastable crystalline zirconium phosphonate. Chemical Communications, 2021, 57(68): 8452–8455 https://doi.org/10.1039/D1CC02446A
18
X Tang , S Wang , Z Zhang , Z Li , L Wang , L Yuan , B Wang , J Sun , L Zheng , H Wang . et al.. Graphene oxide/chitosan/potassium copper hexacyanoferrate(II) composite aerogel for efficient removal of cesium. Chemical Engineering Journal, 2022, 444: 136397 https://doi.org/10.1016/j.cej.2022.136397
19
S Vashnia , H Tavakoli , R Cheraghali , H Sepehrian . Supporting of lead hexacyanoferrate on mesoporous MCM-41 and its use as effective adsorbent for strontium: equilibrium, kinetic, and thermodynamic studies. Separation Science and Technology, 2014, 49(2): 241–248 https://doi.org/10.1080/01496395.2013.828310
H S Hassan , O A A Moamen , W F Zaher . Adaptive neuro-fuzzy inference system analysis on sorption studies of strontium and cesium cations onto a novel impregnated nano-zeolite. Advanced Powder Technology, 2020, 31(3): 1125–1139 https://doi.org/10.1016/j.apt.2019.12.031
23
R M Barrer , R F Bartholomew , L V C Rees . Ion exchange in porous crystals, Part I. self- and exchange-diffusion of ions in chabazites. Journal of Physics and Chemistry of Solids, 1963, 24(1): 51–62 https://doi.org/10.1016/0022-3697(63)90041-6
24
A M El-Kamash . Evaluation of zeolite A for the sorptive removal of Cs+ and Sr2+ ions from aqueous solutions using batch and fixed bed column operation. Journal of Hazardous Materials, 2008, 151(2-3): 432–445 https://doi.org/10.1016/j.jhazmat.2007.06.009
25
A Merceille , E Weinzaepfel , Y Barré , A Grandjean . The sorption behaviour of synthetic sodium nonatitanate and zeolite A for removing radioactive strontium from aqueous wastes. Separation and Purification Technology, 2012, 96: 81–88 https://doi.org/10.1016/j.seppur.2012.05.018
26
H Mimura , T Kanno . Distribution and fixation of cesium and strontium in zeolite A and chabazite. Journal of Nuclear Science and Technology, 1985, 22(4): 284–291 https://doi.org/10.1080/18811248.1985.9735658
27
B Said , A Grandjean , Y Barre , F Tancret , F Fajula , A Galarneau . LTA zeolite monoliths with hierarchical trimodal porosity as highly efficient microreactors for strontium capture in continuous flow. Microporous and Mesoporous Materials, 2016, 232: 39–52 https://doi.org/10.1016/j.micromeso.2016.05.036
28
H RobsonK P Lillerud. Verified Synthesis of Zeolitic Materials, 2nd. rev. ed. International Zeolite Association. Amsterdam, Netherlands, 2001
29
H Awala , J P Gilson , R Retoux , P Boullay , J M Goupil , V Valtchev , S Mintova . Template-free nanosized faujasite-type zeolites. Nature Materials, 2015, 14(4): 447–451 https://doi.org/10.1038/nmat4173
30
S Mintova , M Jaber , V Valtchev . Nanosized microporous crystals: emerging applications. Chemical Society Reviews, 2015, 44(20): 7207–7233 https://doi.org/10.1039/C5CS00210A
31
C Zhang , Q Wu , C Lei , S Han , Q Zhu , S Maurer , D Dai , A N Parvulescu , U Müller , X Meng . et al.. An efficient, rapid, and non-centrifugation synthesis of nanosized zeolites by accelerating the nucleation rate. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2018, 6(42): 21156–21161 https://doi.org/10.1039/C8TA07171C
32
S K Lagergren . About the theory of so-called adsorption of soluble substances. Sven. Vetenskapsakad. Handingarl, 1898, 24: 1–39
W J Jr Weber , J C Morris . Kinetics of adsorption on carbon from solution. Journal of the Sanitary Engineering Division, 1963, 89(2): 31–59 https://doi.org/10.1061/JSEDAI.0000430
35
Z Xue , J Ma , W Hao , X Bai , Y Kang , J Liu , R Li . Synthesis and characterization of ordered mesoporous zeolite LTA with high ion exchange ability. Journal of Materials Chemistry, 2012, 22(6): 2532–2538 https://doi.org/10.1039/C1JM14740D
36
S J Datta , W K Moon , D Y Choi , I C Hwang , K B Yoon . A novel vanadosilicate with hexadeca-coordinated Cs+ ions as a highly effective Cs+ remover. Angewandte Chemie, 2014, 126(28): 7331–7336 https://doi.org/10.1002/ange.201402778
37
H Yang , M Luo , L Luo , H Wang , D Hu , J Lin , X Wang , Y Wang , S Wang , X Bu . et al.. Highly selective and rapid uptake of radionuclide cesium based on robust zeolitic chalcogenide via stepwise ion-exchange strategy. Chemistry of Materials, 2016, 28(23): 8774–8780 https://doi.org/10.1021/acs.chemmater.6b04273
38
H C Thomas . Heterogeneous ion exchange in a flowing system. Journal of the American Chemical Society, 1944, 66(10): 1664–1666 https://doi.org/10.1021/ja01238a017
39
W Loewenstein . The distribution of aluminum in the tetrahedral of silicates and aluminates. American Mineralogist, 1954, 39(1–2): 92–96
40
H Wang , B A Holmberg , Y Yan . Synthesis of template-free zeolite nanocrystals by using in situ thermoreversible polymer hydrogels. Journal of the American Chemical Society, 2003, 125(33): 9928–9929 https://doi.org/10.1021/ja036071q
41
Y Ishikawa , S Tsukimoto , K S Nakayama , N Asao . Ultrafine sodium titanate nanowires with extraordinary Sr ion-exchange properties. Nano Letters, 2015, 15(5): 2980–2984 https://doi.org/10.1021/nl504820c
42
C Liu , L Chen , Z Ye , C Li , X Yin , X Wang , Y Wei . Pellet silica-based titanate adsorbents with high selectivity for strontium removal from synthetic radioactive solutions. Journal of Sol-Gel Science and Technology, 2019, 91(2): 273–285 https://doi.org/10.1007/s10971-019-05005-3
43
J Zhang , L Chen , X Dai , L Zhu , C Xiao , L Xu , Z Zhang , E V Alekseev , Y Wang , C Zhang . et al.. Distinctive two-step intercalation of Sr2+ into a coordination polymer with record high 90Sr uptake capabilities. Chem, 2019, 5(4): 977–994 https://doi.org/10.1016/j.chempr.2019.02.011
44
M Zhang , P Gu , S Yan , L Dong , G Zhang . Na/Zn/Sn/S (NaZTS): quaternary metal sulfide nanosheets for efficient adsorption of radioactive strontium ions. Chemical Engineering Journal, 2020, 379: 122227 https://doi.org/10.1016/j.cej.2019.122227
45
X Zhao , Q Meng , G Chen , Z Wu , G Sun , G Yu , L Sheng , H Weng , M Lin . An acid-resistant magnetic Nb-substituted crystalline silicotitanate for selective separation of strontium and/or cesium ions from aqueous solution. Chemical Engineering Journal, 2018, 352: 133–142 https://doi.org/10.1016/j.cej.2018.06.175
