Abstract
Photocatalytic nitrogen fixation under ambient conditions offers a sustainable alternative to the energy-intensive Haber-Bosch process, yet remains limited by the inertness of N≡N bonds and sluggish multi-electron/proton transfer kinetics. Nature's nitrogenase enzymes, featuring the FeMo cofactor and ATP-driven electron cascades, inspire a new generation of artificial systems capable of mimicking their catalytic precision and selectivity. This review systematically summarizes recent advances in bio-inspired photocatalytic nitrogen reduction, focusing on six key strategies derived from enzymatic mechanisms: Fe-Mo-S active site reconstruction, hierarchical electron relay pathways, ATP-mimicking energy modules, defect-induced microenvironments, interfacial charge modulation, and spatial confinement engineering. While notable progress has been made in enhancing activity and selectivity, challenges remain in dynamic regulation, mechanistic elucidation, and system-level integration. Future efforts should prioritize operando characterization, adaptive interface design, and device-compatible catalyst platforms. By abstracting nature's catalytic logic into synthetic architectures, biomimetic photocatalysis holds great promise for scalable, green ammonia production aligned with global decarbonization goals.