Synergistic Coupling of Intrinsic Internal Electric Field and Macroscopic Polarization in a Photocatalytic Fuel Cell...

The concurrent challenges of environmental pollution and energy scarcity necessitate advanced sustainable technologies. Photocatalytic fuel cells (PFCs) offer a promising route by coupling pollutant degradation with energy recovery. However, the synergistic interplay between anode intrinsic properties and macroscopic polarization effects remains inadequately understood. Herein, a BiOBr-doped TiO₂ nanotube array photoanode with engineered oxygen vacancies was developed to construct a synergistically enhanced PFC system. XPS, EPR, and DFT analyses confirm the formation of oxygen vacancies and favorable band bending, inducing an internal electric field that markedly promotes charge separation and interfacial reaction kinetics. As a result, the charge separation efficiency is enhanced by approximately fourfold relative to pristine TiO₂ nanotube arrays. Under the combined action of the internal electric field and self-bias-induced polarization field, photogenerated electrons and holes undergo directional transport and effective utilization. The optimized PFC achieves 78% sulfamethoxazole degradation within 180 min, representing a 1.38-fold improvement. Degradation pathways and toxicity evolution were further elucidated using LC-MS and Fukui function analysis, highlighting the critical role of electric field-driven charge regulation in high-performance PFCs.