Unveiling the exciton dissociation dynamics steered by built-in electric fields in conjugated microporous polymers for photoreduction of uranium (VI) from seawater.

ABSTRACT

Developing highly efficient photocatalysts based on conjugated microporous polymers (CMPs) are often impeded by the intrinsically large exciton binding energy and sluggish charge transfer kinetics that result from their vulnerable driving force. Herein, a family of pyrene-based nitrogen-implanted CMPs were constructed, where the nitrogen gradient was regulated. Accordingly, the built-in electric field endowed by the nitrogen gradient dramatically accelerates the dissociation of exciton into free carriers, thereby enhancing charge separation efficiency. As a result, PyCMP-3N generated by polymerization of 1,3,6,8-tetrakis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene and 2,4,6-tris(4-bromophenyl)-1,3,5-triazine featured an optimized built-in electric field and exhibited the highest photocatalytic removal efficiency of uranium (VI) (99.5 %). Our proposed strategy not only provides inspiration for constructing the built-in electric field by controlling nitrogen concentration gradients, but also offers an in-depth understanding the crucial role of built-in electric field in exciton dissociation and charge transfer, efficiently promoting CMPs photocatalysis.