Phosphorus cation substitution in TiO2 nanorods toward enhanced N2 electroreduction

[Display omitted] •Phosphorus cation is an effective dopant to enhance NRR performance.•The P-doped TiO2 nanorod was used as a NRR electrocatalyst.•P cation is favorable for oxygen vacancies formation. Electroreduction of N2 into NH3 (NRR) under ambient conditions is an attractive alternative compared to the Haber-Bosch process. However, high activity catalyst is still desired for N2 fixation. Herein, we report for the first time nonmetal phosphorus cation (P) is an effective dopant to enhance NRR performance of TiO2. In 0.1 M LiClO4, P-doped TiO2 nanorods lead to excellent NRR performance with a highest FE of 12.26% and a larger NH3 production rate of 23.05 µg h−1 mgcat.−1. Density function theory calculations disclose that P cation substitution is favorable for oxygen vacancy formation in TiO2 (1 1 0) and Ti3+ is active site for N2 fixation.