Facilitating charge separation and migration of conjugated microporous polymers via skeleton isomerism engineering for photocatalytic reduction of uranium (VI)

Photoreduction of highly toxic and high-mobility UVI into insoluble UIV via conjugated microporous polymers (CMPs) is an effective way to extract uranium from highly acidic wastewater. Nevertheless, undesirable charge separation and migration, as well as rapid reverse charge recombination resulted in unsatisfactory photocatalytic activity of most CMPs. Herein, a pair of D-A CMPs for uranium photocatalytic reduction was developed by modulating skeleton isomerism through isomeric building blocks, named PQ-TPM (with phenanthrenequinone skeleton) and AQ-TPM (with anthraquinone skeleton). Interestingly, compared with anthraquinone skeleton CMP, phenanthrenequinone skeleton CMP can inhibit reverse charge recombination while promoting charge separation and migration due to its stronger built-in electric field and larger dipole moment. Therefore, PQ-TPM achieves an ultra-high photocatalytic UVI removal efficiency of 80.0 % within 180 min visible-light irradiation even under strongly acidic conditions (pH = 2), which was superior to AQ-TPM (30.0 %) and most reported CMPs. This study provides an unconventional concept and an emerging strategy for exploring outstanding CMPs photocatalysts for efficient processing of radionuclides.