To avoid the energy‐consuming step of direct N≡N bond cleavage, photocatalytic N2 fixation undergoing the associative pathways has been developed for mild‐condition operation. However, it is a fundamental yet challenging task to gain comprehensive understanding on how the associative pathways (i.e., alternating vs. distal) are influenced and altered by the fine structure of catalysts, which eventually holds the key to significantly promote the practical implementation. Herein, we introduce Fe dopants into TiO2 nanofibers to stabilize oxygen vacancies and simultaneously tune their local electronic structure. The combination of in situ characterizations with first‐principles simulations reveals that the modulation of local electronic structure by Fe dopants turns the hydrogenation of N2 from associative alternating pathway to associative distal pathway. This work provides fresh hints for rationally controlling the reaction pathways toward efficient photocatalytic nitrogen fixation.

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