Enzymatic Pathway: a Promising Photocatalytic Nitrogen Fixation Reaction Mechanism

Abstract Developing biomimetic catalysts that replicate the nitrogenase functionality for ambient‐condition NH 3 synthesis is a key goal of catalysis research. Recently, the enzymatic pathway with “side‐on” N 2 adsorption is proposed for efficient photocatalytic N 2 fixation. The “side‐on” mode involves the simultaneous bonding of both N atoms to active sites, enabling the enzymatic pathway with strong N 2 adsorption and low energy barrier. Here, recent advances in photocatalytic N 2 fixation via the enzymatic pathway are reviewed in terms of material design and reaction mechanism. The feasibility of regulating the N 2 ‐fixation reaction pathway is demonstrated by summarizing the latest research on defect regulation, doping strategies, and surface engineering used to realize the enzymatic pathway. The effects of the N 2 adsorption mode, charge transfer kinetics, and Gibbs free energy on photocatalytic N 2 fixation via the enzymatic pathway are then comprehensively analyzed to elucidate the relationship between the reaction pathway and N 2 fixation performance, which offers insights into the design of novel photocatalysts. Finally, an outlook on the challenges and future developments related to the enzymatic pathway of photocatalytic N 2 fixation is presented. Bridging material innovation with mechanistic insights can accelerate the realization of practical photocatalytic systems for N 2 fixation through the enzymatic pathway.