Selective solid-phase extraction of trace thorium(IV) using surface-grafted Th(IV)-imprinted polymers with pyrazole derivative

A new pyrazole derivative 1-phenyl-3-methylthio-4-cyano-5-acrylicacidcarbamoyl-pyrazole (PMTCAACP) was synthesized and chosen as a complexing monomer for the preparation of surface-grafted ion-imprinted polymers for selective solid-phase extraction of thorium(IV). The silica gel, modified with maleic anhydride, was prepared as a carrier material. In the ion-imprinting process, Th(IV) was complexed with PMTCAACP, and then imprinted in the polymers grafted to the surface of modified silica gel. Subsequently, the template Th(IV) ions were removed with 6 mol/L HCl solution. The obtained ion-imprinted particles for Th(IV) showed specific recognition, and rapid adsorption and desorption kinetics process. The maximum static and total dynamic adsorption capacity of the ion-imprinted polymers (IIPs) for Th(IV) was 64.8 and 37.4 mg/g, respectively. The relative selectivity coefficient values of the imprinted adsorbent for Th(IV)/U(VI), Th(IV)/Ce(III), Th(IV)/La(III), and Th(IV)/Zr(IV) were 72.9, 89.6, 93.8, and 137.2 times greater than non-imprinted matrix, respectively. The interference effect of common cations tested did not interfere with the recovery of Th(IV). The enhancement factor of 20.2, the detection limit of 0.43 μg/L, and the precision of 2.47% (n = 7) of the method under the optimized conditions were obtained. Additionally, the calibration curve (r = 0.9993) was linear in the range of 1.43–103 μg/L of thorium(IV). The prepared IIPs were shown to be promising for solid-phase extraction coupled with UV–vis spectrophotometry for determination of trace Th(IV) in real samples.