Bio-Inspired Photocatalytic Nitrogen Fixation: From Nitrogenase Mimicry to Advanced Artificial Systems
Wenpin Xia, Kaiyang Zhang, Jiewen Hou, Hongzhu Fu, Mingming Gao, Hui‐Zi Huang, Li‐Wei Chen, Suqin Han, Yen Leng Pak, Hongyu Mou, Xing Gao, Zhenbin Guo
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.