RSC Advances View Article Online PAPER View Journal | View Issue Achieving highly efficient and selective cesium extraction using 1,3-di-octyloxycalix[4]arene- Cite this: RSC Adv.,2021,11,21323 crown-6 in n-octanol based solvent system: experimental and DFT investigation† Kankan Patra,*a Biswajit Sadhu,b Arijit Sengupta, *cd C. B. Patil,a R. K. Mishrade and C. P. Kaushikde 137 Due to the long half-life of Cs (t1/2 30 years), the selective extraction of cesium (Cs) from high level liquid waste is of paramount importance in the back end of the nuclear fuel cycle to avoid long term surveillance of high radiotoxic waste. As 1,3-di-octyloxycalix[4]arene-crown-6 (CC6) is suggested to be a promising candidate for selective Cs extraction, the improvement in the Cs extraction efficiency by CC6 has been investigated through the optimization of the effect of dielectric media on the extraction process. The effects of the feed acid (HNO3, HCl, and HClO4) and the composition of the diluents for Creative Commons Attribution-NonCommercial 3.0 Unported Licence. the ligand in the organic phase on the extraction efficiency of Cs have been investigated systematically. In 100% n-octanol medium, Cs is found to form a 1 : 1 ion-pair complex with CC6 (0.03 M) providing a very high distribution ratio of DCs 22, suggesting n-octanol as the most suitable diluent for Cs extraction. No significant interference of other relevant cations such as Na, Mg and Sr was observed on the DCs value in the optimized solvent system. Density functional theory (DFT) based calculations have been carried out to elucidate the reason of ionic selectivity and enhanced Cs extraction efficiency of Received 5th April 2021 CC6 in the studied diluent systems. In addition to the ionic size-based selectivity of the crown-6 cavity, Accepted 31st May 2021 the polarity of the organic solvent system, the hydration energy of the ion, and the relative DOI: 10.1039/d1ra02661e This article is licensed under a reorganization of CC6 upon complexation with Cs are understood to have roles in achieving the rsc.li/rsc-advances enhanced efficiency for the extraction of Cs by the CC6 extractant in nitrobenzene medium. Open Access Article. Published on 16 June 2021. Downloaded 9/26/2021 6:08:56 AM. well established that these two major radio nuclides, i.e. 137Cs 1. Introduction 90 (half-life, t1/2 ¼ 30.1 years) and Sr (half-life, t1/2 ¼ 28.9 years), are Asignicant amount of radioactivity in the high-level liquid waste mainly responsible for the heat and radiation load of the HLW. obtained from the nuclear fuel recycling process is due to the Furthermore, due to high mobility of Cs, the radionuclide might – presence of the 137Cs radionuclide in the solution. Secure pose a long-term unpleasant impact on the ecology.2 10 management of these nuclear waste solutions is one of the most The main concept behind the separation of a metal ion into signicant technological and industrial challenges faced by the an organic phase through solvent extraction is the screening of nuclear industry. The success and public acceptance of the nuclear the charge on the metal ion through suitable complexation power program are highly dependent on the successful removal of followed by the mass transfer into the nonpolar organic phase. the harmful radionuclides from the radioactive nuclear waste. The lower ionic potential of Cs+ makes it difficult to undergo Aer separation of minor actinides, collectively, 99% of the complexation with conventional ligands and hence leaves us remaining radioactivity of the high-level waste (HLW) solution is with the only choice of complexation based on the size selec- mainly attributed to 137Cs and 90Sr present in the solution.1 It is tivity of the macrocyclic cavities of the extractant molecules. A variety of solid phase sorbents have been reported in literature for the effective separation of heavy metals from aNuclear Recycle Board, Bhabha Atomic Research Centre, Tarapur 401504, India. different aqueous streams.11 Multiwall carbon nanotubes E-mail: [email protected] bHealth Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085, India functionalized with thorium oxide (MWCNTs/ThO2) was re- ff 2+ cRadiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India. ported for e ective adsorption of Pb ions (sorption 93.8%) + 12 E-mail: [email protected] from aqueous system due to the removal of H ions. Naushad dHomi Bhabha National Institute, Anushaktinagar, Mumbai 400 094, India et al. reported magnetic metal–organic framework for the e 2+ 4+ Nuclear Recycle Group, Bhabha Atomic Research Centre, Mumbai 400 085, India removal of UO2 and Th with adsorption capacity of 227.3 À † Electronic supplementary information (ESI) available. See DOI: and 285.7 mg g 1, respectively.13 Iron based nanocomposite was 10.1039/d1ra02661e © 2021 The Author(s). Published by the Royal Society of Chemistry RSC Adv.,2021,11,21323–21331 | 21323 View Article Online RSC Advances Paper reported to remove heavy metals including Cd2+,Cr3+ and Co2+ note to their toxicity, use of nitrobenzene and 1,2-dichloroethane is effectively.14 Alqadami et al. reported Pb2+ sorption on nano- usually avoided in the back end nuclear fuel cycle. composite using carboxylic and amino functionalities.15 Based on these understandings in the reported litera- Naushad et al.16 also reported curcumin based magnetic nano- ture,25,38,39 in the present study we have explored the experi- composite as highly efficient solid phase extractant for Hg2+ mental conditions, especially through the use of varying À with a capacity of 144.9 mg g 1. Khan et al. reported the utili- dielectric media as the diluents for the ligand in the organic zation of hydrochar for the removal of heavy metals including phase, aiming to achieve signicantly enhanced distribution 2+ 2+ 17,18 Pb and Cd . Nanomagnetic copper ferrite/drumstick pod ratio (DCs) for the Cs extraction, employing the well-known CC6 biomass (CuFe2O4/DC) composite has also been employed for ligand as the complexing agent. We have analysed the inu- removal of Pb2+ predominantly following Langmuir isotherm19 ences of several solvent systems of varying dielectric properties Penicillium chrysogenum and Aspergillus ustus were reported to on the DCs values for Cs extraction using CC6 as the extractant. separate Cd2+,Cu2+ and Pb2+ from aqueous medium.20 Based on our study, n-octanol is projected to be an appropriate The Cs-selective extractants, especially those in the dielectric medium for CC6 to provide maximum Cs extraction calixarene-crown-6 and the calixarene-bis-(crown-6) families, efficiency. Effects of different mineral acids and interference of have been known for decade now.21–30 Different extraction relevant alkali and alkaline earth metal ions (Na+,Mg2+,Sr2+)on methods for the recovery of 137Cs have been reported in the the recovery of Cs+ have also been systematically investigated. literature based on these crown based systems.31–33 Calix crown Furthermore, to decipher the structures, binding motifs and ether have been introduced as a strong extracting agent for the energetics of the metal–CC6 complexes formed under different alkali/alkaline earth metal cations, because of the presence of experimental conditions, the DFT based calculations have also suitable pre-organised cavity in the structural frameworks of been carried out to get a better insight of the studied systems. these ligands.34–37 The complexation selectivity for the metal ions by these ligands depends largely on the conformation Creative Commons Attribution-NonCommercial 3.0 Unported Licence. adopted by the rigidi ed calix[4]arene moieties of these mole- 2. Experimental cules. The partial cone isomer of 1-3-dimethoxy-p-terbutylcalix 2.1 Materials [4]arene-crown-5 has been established for the selective separa- tion of potassium ion.38 Similarly, Casnati et al.25 synthesized CC6 ligand was synthesized following the procedure reported by 25 and reported another calix-crown based ligand, namely 1,3-di- Casnati et al., which was further puri ed and characterized in- 25 octyloxycalix[4]arene-crown-6 (CC6) which was found to be house. Casnati et al. reported 1,3-dialkoxycalix[4]arene-crown- highly Cs selective. Further, Sharma et al.39 optimized the 6 ionophores are obtained in the xed 1,3-alternate conforma- – composition of the diluent system for the organic phase based tion in 63 85% yield, hence further puri cations were carried on dodecane and iso-decyl alcohol to efficiently extract Cs+ out to avoid the side product interference to the reaction This article is licensed under a medium. At the same time to avoid the acidic impurity and to using 0.03 M CC6 and obtained the DCs value as 6.6. Understanding the mechanistic aspects of the metal extrac- reduce the background noise. Chemical formula and geometry tion processes is very essential in the nuclear waste manage- optimized structure of CC6 ligand are shown Fig. 1. The radiotracer 137Cs was used in the present investigation and Open Access Article. Published on 16 June 2021. Downloaded 9/26/2021 6:08:56 AM. ment program. In this respect, the density functional theory (DFT) method is currently widely used40,41 which is an appro- procured from Board of Radiation and Isotope Technology 137 priate level of calculation can comprehensively provide molec- (BRIT), India. Cs radiotracer was used throughout the ffi ular level insights of the experimentally obtained results on the experiment for evaluating extraction e ciency. During the selective extraction processes by different ligand systems. For instance, Ali and coworkers42 have reported an unusually high selectivity of Cs+ in a calix-crown based ligand using DFT calculations.