Synergistic Interplay between Surface Polarons and Adsorbates for Photocatalytic Nitrogen Reduction on TiO$_2$(110)

Abstract

Photocatalytic nitrogen reduction under ambient conditions represents a promising pathway toward sustainable ammonia production. However, the fundamental mechanisms, particularly the role of photogenerated charge carriers and their interactions with surface defects and adsorbates, remain elusive. Here, we employ density functional theory with Hubbard U corrections and hybrid functionals to demonstrate that the synergistic interactions between photogenerated electron polarons and point defects are essential for enabling nitrogen reduction on TiO$_2$(110). We reveal that water adsorption promotes polaron migration from subsurface to surface sites, while subsequent water dissociation stabilizes polarons near oxygen vacancies through proton coupled electron polaron transfer (PCEpT). This surface localization of polarons is critical for effective N$_2$ adsorption and activation. Our findings are consistent with previous experimental reports utilizing EPR that confirm the presence of reduced Ti species and STM, which shows the presence of water dimers on the surface. Moreover, the simultaneous interaction between polarons and reaction intermediates facilitates polaron transfer, thereby driving the completion of the nitrogen reduction reaction. Our findings elucidate the pivotal role of surface polarons in photocatalytic nitrogen fixation and provide mechanistic insights applicable to a broad range of oxide surfaces and interfaces capable of hosting small polarons, offering new design principles for efficient photocatalysts operating under ambient conditions.