Greatly Enhanced Electrocatalytic N2 Reduction on TiO2 via V Doping

As a sustainable alternative technology to the Haber-Bosch process, electrochemical N-2 reduction offers the hope of directly converting N-2 to NH3 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 TiO2 toward ambient N-2-to-NH3 fixation with excellent selectivity is reported. In 0.5 m anhydrous lithium perchlorate, V-doped TiO2 nanorods attain a high Faradic efficiency of 15.3% and a large NH3 yield of 17.73 mu g 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.