Greatly Enhanced Electrocatalytic N2 Reduction on TiO2 via V Doping

Abstract As a sustainable alternative technology to the Haber–Bosch process, electrochemical N 2 reduction offers the hope of directly converting N 2 to NH 3 at ambient conditions. However, its efficiency greatly depends on screening high‐active electrocatalysts for the N 2 reduction reaction (NRR). Here, the recent experimental finding that V is an effective dopant to greatly improve the NRR performances of TiO 2 toward ambient N 2 ‐to‐NH 3 fixation with excellent selectivity is reported. In 0.5 m anhydrous lithium perchlorate, V‐doped TiO 2 nanorods attain a high Faradic efficiency of 15.3% and a large NH 3 yield of 17.73 µg h −1 mg cat. −1 at −0.40 and −0.50 V versus reversible hydrogen electrode, respectively, rivaling the performances of most reported aqueous‐based NRR electrocatalysts. Density function theory (DFT) calculations are performed to gain further insight into the catalytic mechanism.