Synthesis and characterization of non-porous amorphous polymers for enhanced iodine adsorption
Mengqi Wang A # , Henglong Tang A # , Zhu Long A and Chang Sun
A *
A
Handling Editor: Richard Hoogenboom
Abstract
With the increasing demand for sustainable energy sources, the management of radioactive iodine, a byproduct of nuclear energy, has become critical for environmental safety and human health. This study presents the design and synthesis of non-porous amorphous polymers, specifically PEI-PD, derived from polyethylenimine (PEI) and pyromellitic dianhydride (PD), for the adsorption of iodine from aqueous and gaseous environments. The adsorbent exhibits high efficiency in capturing iodine, with a remarkable adsorption capacity of 4.43 g g–1 for volatile iodine and 1.43 g g–1 for liquid iodine. The adsorption process is governed by a pseudo-second-order kinetic model and follows the Langmuir isotherm, indicating a chemisorption mechanism driven by electrostatic attraction. The mechanism of iodine adsorption by the adsorbent was investigated using infrared spectroscopy and independent gradient modeling (IGMH), which helped to clarify types of weak interaction between the adsorbent and iodine and the adsorption sites. The study highlights the potential of PEI-PD as an effective material for the removal of radioactive iodine, contributing to the safe and sustainable management of nuclear waste.
Keywords: adsorption mechanism, environmental safety, IGMH analysis, iodine adsorption, non-porous amorphous polymers, nuclear waste management, PEI-based adsorbent, weak interaction analysis.
References
1 Zou C, Zhao Q, Zhang G, Xiong B. Energy revolution: from a fossil energy era to a new energy era. Nat Gas Ind B 2016; 3: 1-11.
| Crossref | Google Scholar |
2 Cicia G, Cembalo L, Del Giudice T, Palladino A. Fossil energy versus nuclear, wind, solar and agricultural biomass: insights from an Italian national survey. Energy Policy 2012; 42: 59-66.
| Crossref | Google Scholar |
3 Sadekin S, Zaman S, Mahfuz M, Sarkar R. Nuclear power as foundation of a clean energy future: a review. Energy Procedia 2019; 160: 513-518.
| Crossref | Google Scholar |
4 Umadevi K, Mandal D. Performance of radio-iodine discharge control methods of nuclear reprocessing plants. J Environ Radioact 2021; 234: 106623.
| Crossref | Google Scholar | PubMed |
5 Nandanwar SU, Coldsnow K, Utgikar V, Sabharwall P, Aston DE. Capture of harmful radioactive contaminants from off-gas stream using porous solid sorbents for clean environment – a review. Chem Eng J 2016; 306: 369-381.
| Crossref | Google Scholar |
6 Huve J, Ryzhikov A, Nouali H, Lalia V, Augé G, Daou TJ. Porous sorbents for the capture of radioactive iodine compounds: a review. Rsc Adv 2018; 8: 29248-29273.
| Crossref | Google Scholar | PubMed |
7 Jin K, Lee B, Park J. Metal-organic frameworks as a versatile platform for radionuclide management. Coord Chem Rev 2021; 427: 213473.
| Crossref | Google Scholar |
8 Robshaw TJ, Turner J, Kearney S, Walkley B, Sharrad CA, Ogden MD. Capture of aqueous radioiodine species by metallated adsorbents from wastestreams of the nuclear power industry: a review. Sn Appl Sci 2021; 3: 843.
| Crossref | Google Scholar |
9 Yang Y, Tu C, Yin H, Liu J, Cheng F, Luo F. Molecular iodine capture by covalent organic frameworks. Molecules 2022; 27: 9045.
| Crossref | Google Scholar | PubMed |
10 Yu Y-N, Yin Z, Cao L-H, Ma Y-M. Organic porous solid as promising iodine capture materials. J Incl Phenom Macrocycl Chem 2022; 102: 395-427.
| Crossref | Google Scholar |
11 Zhang X, Maddock J, Nenoff TM, Denecke MA, Yang S, Schröder M. Adsorption of iodine in metal–organic framework materials. Chem Soc Rev 2022; 51: 3243-3262.
| Crossref | Google Scholar | PubMed |
12 Lei Y, Zhang G, Zhang Q, et al. Visualization of gaseous iodine adsorption on single zeolitic imidazolate framework-90 particles. Nat Commun 2021; 12: 4483.
| Crossref | Google Scholar | PubMed |
13 Liu Y-J, Sun Y-F, Shen S-H, et al. Water-stable porous Al24 Archimedean solids for removal of trace iodine. Nat Commun 2022; 13: 6632.
| Crossref | Google Scholar | PubMed |
14 Yao S, Fang W-H, Sun Y, Wang S-T, Zhang J. Mesoporous assembly of aluminum molecular rings for iodine capture. J Am Chem Soc 2021; 143: 2325-2330.
| Crossref | Google Scholar | PubMed |
15 Song S, Shi Y, Liu N, Liu F. C═N linked covalent organic framework for the efficient adsorption of iodine in vapor and solution. RSC Adv 2021; 11: 10512-10523.
| Crossref | Google Scholar | PubMed |
16 Gong C-H, Li Z-Y, Chen K-W, Gu A-T, Wang P, Yang Y. Synthesis and characterization of Ag@Cu-based MOFs as efficient adsorbents for iodine anions removal from aqueous solutions. J Environ Radioact 2023; 265: 107211.
| Crossref | Google Scholar | PubMed |
17 Pan T, Yang K, Dong X, Han Y. Adsorption-based capture of iodine and organic iodides: status and challenges. J Mater Chem A 2023; 11: 5460-5475.
| Crossref | Google Scholar |
18 Zhou W, Li A, Zhou M, Xu Y, Zhang Y, He Q. Nonporous amorphous superadsorbents for highly effective and selective adsorption of iodine in water. Nat Commun 2023; 14: 5388.
| Crossref | Google Scholar | PubMed |
19 Atwood JL, Barbour LJ, Jerga A. Storage of methane and freon by interstitial van der Waals confinement. Science 2002; 296: 2367-2369.
| Crossref | Google Scholar | PubMed |
20 Thallapally PK, McGrail BP, Dalgarno SJ, Schaef HT, Tian J, Atwood JL. Gas-induced transformation and expansion of a non-porous organic solid. Nat Mater 2008; 7: 146-150.
| Crossref | Google Scholar | PubMed |
21 Herbert SA, Janiak A, Thallapally PK, Atwood JL, Barbour LJ. Diffusion of vaporous guests into a seemingly non-porous organic crystal. Chem Commun 2014; 50: 15509-15512.
| Crossref | Google Scholar | PubMed |
22 Jie K, Zhou Y, Li E, Huang F. Nonporous adaptive crystals of pillararenes. Acc Chem Res 2018; 51: 2064-2072.
| Crossref | Google Scholar | PubMed |
23 Wu J-R, Yang Y-W. Synthetic macrocycle-based nonporous adaptive crystals for molecular separation. Angew Chem Int Ed Engl 2021; 60: 1690-1701.
| Crossref | Google Scholar | PubMed |
24 Ma Y, Liu W-J, Zhang N, Li Y-S, Jiang H, Sheng G-P. Polyethylenimine modified biochar adsorbent for hexavalent chromium removal from the aqueous solution. Bioresour Technol 2014; 169: 403-408.
| Crossref | Google Scholar | PubMed |
25 Zhu Q, Shentu B, Liu Q, Weng Z. Swelling behavior of polyethylenimine–cobalt complex in water. Eur Polym J 2006; 42: 1417-1422.
| Crossref | Google Scholar |
26 Swamy AY, Prasad S, Pan X, Andersson MR, Gedefaw D. Glutaraldehyde and glyoxal crosslinked polyethylenimine for copper ion adsorption from water. Chemistryselect 2022; 7: e202104318.
| Crossref | Google Scholar |
27 Kumari S, Avais M, Katiyar JD, Suman YK, Chattopadhyay S. Polyethylenimine polyampholytes: synthesis, characterization and dye adsorption study. J Polym Res 2022; 29: 293.
| Crossref | Google Scholar |
28 Jin X, Xiang Z, Liu Q, Chen Y, Lu F. Polyethyleneimine-bacterial cellulose bioadsorbent for effective removal of copper and lead ions from aqueous solution. Bioresour Technol 2017; 244: 844-849.
| Crossref | Google Scholar | PubMed |
29 Nan Y, Gomez-Maldonado D, Whitehead DC, Yang M, Peresin MS. Comparison between nanocellulose–polyethylenimine composites synthesis methods towards multiple water pollutants removal: A review. Int J Biol Macromol 2023; 232: 123342.
| Crossref | Google Scholar | PubMed |
30 Wang Y, Bai X, Zhang X, Li J. Improving CO2 separation performance of PVAm membrane by the addition of polyethylenimine-functionalized halloysite nanotubes. J Membr Sci 2023; 677: 121609.
| Crossref | Google Scholar |
31 Fredin L, Nelander B. Is the benzene-iodine complex really axial? J Am Chem Soc 1974; 96: 1672-1673.
| Crossref | Google Scholar |
32 Sorokin A, Sukhanov P, Popov V, Kannykin S, Lavlinskaya M. A new approach to increasing the equilibrium swelling ratio of the composite superabsorbents based on carboxymethyl cellulose sodium salt. Cellulose 2022; 29: 159-173.
| Crossref | Google Scholar |
33 Xu Y, Wang Q, Wang Y, Hu F, Sun B, Gao T, Zhou G. One-step synthesis of polyethyleneimine-grafted styrene-maleic anhydride copolymer adsorbents for effective adsorption of anionic dyes. Molecules 2024; 29: 1887.
| Crossref | Google Scholar | PubMed |
34 Xie Y, Chen H, Mei B, et al. Highly efficient iodine capture by polyethyleneimine-impregnated CuAl-pillared montmorillonite. J Environ Chem Eng 2023; 11: 110204.
| Crossref | Google Scholar |
35 Li X, Chen G, Jia Q. Highly efficient iodine capture by task-specific polyethylenimine impregnated hypercrosslinked polymers. J Taiwan Inst Chem Eng 2018; 93: 660-666.
| Crossref | Google Scholar |
36 Hijazi A, Azambre B, Finqueneisel G, Vibert F, Blin JL. High iodine adsorption by polyethyleneimine impregnated nanosilica sorbents. Micropor Mesopor Mater 2019; 288: 109586.
| Crossref | Google Scholar |
37 Zhang J, Shi W, Yang M, Huang K, Zhu Y, Xie Z. Modified polyethyleneimine with abundant N/O/S-heteroatoms and aromatic segments: convenient synthesis via sulfur-isocyanide-amine multicomponent reaction and application in high-performance iodine capture. Eur Polym J 2024; 205: 112724.
| Crossref | Google Scholar |
38 Gambhir D, Venkateswarulu M, Verma T, Koner RR. High adsorption capacity of an sp2/sp3-N-rich polymeric network: from molecular iodine capture to catalysis. Acs Appl Polym Mater 2020; 2: 152-158.
| Crossref | Google Scholar |
39 He Y, Jiang B, Chen J, Jiang Y, Zhang YX. Synthesis of MnO2 nanosheets on montmorillonite for oxidative degradation and adsorption of methylene blue. J Colloid Interface Sci 2018; 510: 207-220.
| Crossref | Google Scholar | PubMed |
40 Ma T, Chang PR, Zheng P, Zhao F, Ma X. Fabrication of ultra-light graphene-based gels and their adsorption of methylene blue. Chem Eng J 2014; 240: 595-600.
| Crossref | Google Scholar |
41 Nassar MY, Ahmed IS, Mohamed TY, Khatab M. A controlled, template-free, and hydrothermal synthesis route to sphere-like α-Fe2O3 nanostructures for textile dye removal. Rsc Adv 2016; 6: 20001-20013.
| Crossref | Google Scholar |
