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The present study focuses on the synthesis of phosphate-based ion imprinted polymers (IIPs) using a chemical homologue (cerium(IV)) for the fast and selective separation of Bk(IV) from a large number of fission products. Two imprinted phosphate-based gels, poly(bis[2-(methacryloyloxy)ethyl] phosphate) (poly-BMEP) and poly(bis[2-(methacryloyloxy)ethyl] phosphate-co-acrylic acid) (poly-(BMEP-AA)) have been prepared by in situ UV polymerization. The imprinting has been achieved by complexation of the phosphate-based monomers with the Ce(IV) ion. The desorption of Ce(IV) ions from the imprinted gels has been studied with H2O2. The prepared gels have been characterized by FE-SEM, FT-IR, XRD, and XPS. The imprinted gels have been shown to extract Ce(IV) ions selectively from an 8 mol L–1 HNO3 medium in the presence of fission products (Ba, Ru, Tb). DFT calculations show formation of a 1:4 Ce(IV):BMEP complex. The presence of acrylic acid (AA) has been shown to improve the kinetics of Ce(IV) uptake owing to the decrease in the tortuosity of the polymeric structure due to the AA presence. The imprinted gels though do not show kinetic selectivity toward Ce(IV) compared to non-imprinted gels; they show thermodynamic selectivity toward Ce(IV), indicating the inability of the non-imprinted gels to retain Ce(IV) for longer periods. Also, the imprinted gels have been found to be more selective compared to solvent extraction with BMEP as the complexing agent. These two imprinted gels were used to extract Bk, which was produced in 11B + 238U at a 66 MeV beam energy. The extraction by IIPs have been found to be much faster with the reduction in overall extraction time by ∼80% relative to the earlier reported method though with a lesser selectivity for some elements. The present approach, as guided by DFT calculations, offers a possibility of preparing IIPs for the selective extraction of heavy actinides and trans-actinides using their chemical homologues as the imprinting ion.
The present study focuses on the synthesis of phosphate-based ion imprinted polymers (IIPs) using a chemical homologue (cerium(IV)) for the fast and selective separation of Bk(IV) from a large number of fission products. Two imprinted phosphate-based gels, poly(bis[2-(methacryloyloxy)ethyl] phosphate) (poly-BMEP) and poly(bis[2-(methacryloyloxy)ethyl] phosphate-co-acrylic acid) (poly-(BMEP-AA)) have been prepared by in situ UV polymerization. The imprinting has been achieved by complexation of the phosphate-based monomers with the Ce(IV) ion. The desorption of Ce(IV) ions from the imprinted gels has been studied with H2O2. The prepared gels have been characterized by FE-SEM, FT-IR, XRD, and XPS. The imprinted gels have been shown to extract Ce(IV) ions selectively from an 8 mol L–1 HNO3 medium in the presence of fission products (Ba, Ru, Tb). DFT calculations show formation of a 1:4 Ce(IV):BMEP complex. The presence of acrylic acid (AA) has been shown to improve the kinetics of Ce(IV) uptake owing to the decrease in the tortuosity of the polymeric structure due to the AA presence. The imprinted gels though do not show kinetic selectivity toward Ce(IV) compared to non-imprinted gels; they show thermodynamic selectivity toward Ce(IV), indicating the inability of the non-imprinted gels to retain Ce(IV) for longer periods. Also, the imprinted gels have been found to be more selective compared to solvent extraction with BMEP as the complexing agent. These two imprinted gels were used to extract Bk, which was produced in 11B + 238U at a 66 MeV beam energy. The extraction by IIPs have been found to be much faster with the reduction in overall extraction time by ∼80% relative to the earlier reported method though with a lesser selectivity for some elements. The present approach, as guided by DFT calculations, offers a possibility of preparing IIPs for the selective extraction of heavy actinides and trans-actinides using their chemical homologues as the imprinting ion.
In 1957 Glenn T. Seaborg conceived and advocated for the construction of the High Flux Isotope Reactor (HFIR) and the Transuranium Processing Plant (since then renamed the Radiochemical Engineering Development Center, or REDC) at Oak Ridge National Laboratory. Heavily shielded hot cells, glove boxes, and laboratories allow recovery of transuranium elements produced in substantial quantities. Seaborg’s vision of HFIR and REDC producing milligram quantities of berkelium, californium, and einsteinium has been fulfilled beginning in 1966 through May 2019 with 78 production campaigns yielding a cumulative totals of 1.2 g of 249Bk, 10.2 g of 252Cf, 39 mg of 253Es, and 15 pg of 257Fm. Notably, 252Cf is a neutron source used in many industrial applications including oil exploration; process control systems for the cement industry, coal analysis, and power production; sources to start nuclear reactors and perform nondestructive materials analyses; homeland security and national defense detection devices; and medical research. Isotopes made available through transplutonium production at HFIR/REDC have enabled scientists to study the nuclear properties and reactions, chemical properties, optical properties, and solid-state properties of transplutonium elements. Long-lived isotopes have served as targets in heavy ion accelerators to produce heavier elements leading to the discovery of 104Rf, 105Db, 106Sg, 113Nh, 114Fl, 115Mc, 116Lv, 117Ts, and 118Og. This paper reviews the evolution of the processing flowsheets to produce, separate, and purify transplutonium isotopes, which have evolved over 50 years of operation at HFIR and REDC, and summarizes directions of future work to improve the efficiency of the production operations.
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