Enhancing Stable Electricity Generation and Assimilative Ammonium-N Removal in Photosynthetic Algae–Microbial Fuel Cells Using a Chlorella Biofilm-Loaded ZnO-NiO@rGO Carbon-Fiber Composite Cathode

Photosynthetic algae–microbial fuel cells (PAMFCs) are attractive for energy-positive wastewater treatment and carbon mitigation. However, PAMFC performance under continuous flow is often constrained by limited cathodic electron-acceptor supply and unstable photosynthetic biofilms, while the extent to which cathode interfacial engineering can stabilize diurnal power output and assimilative NH4+–N removal remains unclear. In this study, the sponge-like and petal-like ZnO0.2-NiO@rGO-modified carbon fibers (ZnO0.2-NiO@rGO-pCFs and ZnO0.2-NiO@rGO-pCFp) and pre-fabricated carbon felt (pCF) were used as cathode materials to construct three sets of PAMFC systems. Under light–dark cycling, the engineered cathodes reached steady operation within about 6.5 d and increased the steady-state voltage to approximately 0.35 V, compared with approximately 0.08 V for pCF. Under continuous-flow conditions, cathodic NH4+–N removal exhibited a stable diurnal rhythm, with higher removal during illumination at about 43–51% than in the dark at about 29–30%, consistent with algal assimilation as the primary nitrogen sink, while cathode modification mainly improved the cathodic microenvironment and response stability. Compared with pCF, the ZnO0.2–NiO@rGO cathode enriched a more even, Chlorophyta-dominated algal biofilm with an approximate relative abundance of 80%, indicating that its selective interfacial environment favors biofilm stabilization and sustains in situ oxygen production and cathodic electron-acceptor supply. Consequently, the composite cathode enhanced voltage output and stabilized light-enhanced, assimilative NH4+–N removal under aeration-free operation, while establishing an interpretable link between electrochemical performance and 18S rDNA-derived community assembly features, thereby providing a low-cost cathode design basis for nitrogen removal in wastewater treatment.