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.