Unraveling Synergistic Effect of Defects and Piezoelectric Field in Breakthrough Piezo‐Photocatalytic N2 Reduction

Piezo-photocatalysis is a frontier technology for converting mechanical and solar energies into crucial chemical substances and has emerged as a promising and sustainable strategy for N2 fixation. Here, for the first time, defects and piezoelectric field are synergized to achieve unprecedented piezo-photocatalytic nitrogen reduction reaction (NRR) activity and their collaborative catalytic mechanism is unraveled over BaTiO3 with tunable oxygen vacancies (OVs). The introduced OVs change the local dipole state to strengthen the piezoelectric polarization of BaTiO3 , resulting in a more efficient separation of photogenerated carrier. Ti3+ sites adjacent to OVs promote N2 chemisorption and activation through d-π back-donation with the help of the unpaired d-orbital electron. Furthermore, a piezoelectric polarization field could modulate the electronic structure of Ti3+ to facilitate the activation and dissociation of N2 , thereby substantially reducing the reaction barrier of the rate-limiting step. Benefitting from the synergistic reinforcement mechanism and optimized surface dynamics processes, an exceptional piezo-photocatalytic NH3 evolution rate of 106.7 µmol g-1 h-1 is delivered by BaTiO3 with moderate OVs, far surpassing that of previously reported piezocatalysts/piezo-photocatalysts. New perspectives are provided here for the rational design of an efficient piezo-photocatalytic system for the NRR.