A subnanoscale dynamic-integrated catalytic system for bioinspired photoelectrochemical ammonia synthesis

Photoelectrochemical nitrogen (N) fixation to ammonia (NH ₃ ) is a sustainable route for hydrogen storage yet limited by the stubborn N≡N bond and competitive interfacial reaction kinetics. Inspired by nitrogenase, we design single-atom iron (Fe)–doped tungsten oxide (WO ₃ ) subnanowires as a bioinspired, dynamically integrated catalytic platform to systematically overcome these challenges: (i) The distorted lattice and asymmetric sites create a dynamically responsive catalytic center, where photoinduced valence-lattice oscillation drives electron delocalization, shifting the conventional N ₂ adsorption mode and reaction pathway; (ii) the unique self-adhesive and film-forming properties enable robust, binder-free electrodes with maximized active-site exposure; and (iii) surface ligand engineering establishes a bioinspired microenvironment that selectively enriches N ₂ and regulates proton access. This system achieves an NH ₃ yield of 286 micrograms per milligram of catalyst per hour, a 24-fold improvement over conventional Fe-WO ₃ nanowires, with stable performance over 30 cycles. This work demonstrates functionally integrated, bioinspired catalysis at the subnanoscale, offering a paradigm for efficient molecular conversion.