Modulating conjugated microporous polymers via cyclization as a remarkable photo-enhanced uranium recovery platform

Uranium recovery is of great significance for managing environmental contamination, improving the utilization rate of uranium resources, reducing the pressure of nuclear fuel supply and building a closed-loop nuclear fuel cycle system. However, most of the current adsorbents are limited in practical application due to their poor selectivity in highly acidic environments (pH = 1). Here, we present a powerful uranium recovery strategy with combined ligand complexation, chemical reduction and photoreduction based on metal-free cyclization-modulated conjugated microporous polymers (CMPs). Our well-tailored CMP (CTATP-DHBA) is rich in pyridine and hydroquinone units, forming favorable six-membered chelation motifs to be well suited for selective loading and reduction of U^VI, thus exhibiting remarkable uranium removal efficiency (ca. 83.27% removal in 200 ppm solutions, pH = 1). In the dark, CTATP-DHBA can effectively reduce pre-enriched U^VI to U^IV in situ via hydroquinone units on the skeleton, thus weakening the proton competition and achieving excellent uranium recovery efficiency. Meanwhile, the synergistic effect of the cyclized π-conjugated skeleton and the oxidized benzoquinone units significantly enhances the photocatalytic activity of CTATP-DHBA, and an additional U^VI photocatalytic reduction can occur under visible light irradiation, enabling photo-enhanced uranium recovery. ENVIRONMENTAL IMPLICATION: The mineralization of valence-variable radionuclides such as uranium could not only enhance the extraction performance and simplify the subsequent separation procedure, but also effectively weaken the competition of protons for selective sites in the acidic sample matrix. Thus, the construction of robust CMPs with excellent photoreduction activity and affinity may be an ideal material for the selective extraction and in-situ mineralization of strategic nuclide uranium from strongly acidic radioactive wastewater. Herein, a metal-free cyclization-modulated CMP with the favorable six-membered chelation motifs is tailor-made as an efficient platform for efficient extraction and in situ mineralization of valence-variable nuclide uranium.