Periodic Paradigm in Nitrogen Reduction Catalysis: Fundamentals and Advances

Abstract The escalating global energy demand has intensified the pursuit of sustainable fuel alternatives, with nitrogen (N₂) reduction to ammonia (NH₃) emerging as a promising route toward achieving energy security and climate resilience, though not without formidable scientific and technical challenges. The extreme chemical inertness of N 2 renders its conversion highly energy‐intensive, with the conventional Haber–Bosch process operating under harsh conditions (300–500 °C, 20–30 MPa) and resulting in significant greenhouse gas (GHG) emissions as an environmental trade‐off. However, with the rise of sustainable energy research, green pathways for NH 3 synthesis have gained momentum, utilizing photocatalytic, electrocatalytic, and photo‐electrocatalytic approaches to drive N 2 reduction under mild, solar‐powered conditions. Although, the process comes with a disadvantage of low conversion efficiencies and light‐absorption tendencies of catalyst which can get better with potential heterostructure formation and surface‐interface modulations. This review focuses on the progress of NH 3 synthesis via potential catalytic systems and heterostructures, along with their challenges and prospects. Moreover, this review offers insight into designing and optimizing of photocatalysts and electrocatalysts toward N 2 fixation. This review aims to invigorate research in the emerging yet underexplored field of NRR, contributing meaningfully toward sustainable development and environmental stewardship.