Asymmetric Co ₁ N ₃ P ₁ Cathode with High HER Activity Enabling Boosted Simultaneous Uranium Recovery and Organics Degradation in an Internal‐Drives Enhanced Photocatalytic Fuel Cell System

Abstract Uranium is an essential element as both fission fuel and radioactive waste. Therefore, the recovery of uranium is of great importance. Here, an internal enhanced photocatalytic fuel cell (IEPFC) system is proposed to achieve high‐efficiency uranium extraction performance through the hydrogen evolution reaction (HER) process. An asymmetric Co 1 N 3 P 1 , derived from phosphorated ZIF‐67 grown on carbon felt (Co 1 N 3 P 1 C/CF), is utilized as a cathode and demonstrates excellent HER performance. A front FTO glass‐based TiO 2 nanorod (TNR) film and a rear‐placed Si photovoltaic cell (Si PVC) serve as an integrated photoanode. Thanks to the high HER performance of the Co 1 N 3 P 1 cathode and the enhanced internal drive of the photoanode, both the uranium recovery efficiency and the organic tetracycline (TC) degradation rate can reach 100% within 40 min of illumination. X‐ray absorption near‐edge structure (XANES) and density functional theory (DFT) calculations reveal that the Co 1 N 3 P 1 possesses a positive synergistic effect between HER and uranium recovery. This enhancement is due to the modified electronic structure resulting from the incorporation of P, and the robust adsorption between U and OH * promoted by electron transfer interactions between U and N and P. This work opens a new opportunity for the recovery of uranium from the complex water bodies.