Effects of Molybdenum Doping on the Enhanced Electrocatalytic Nitrogen Reduction Reaction Performance of CeO2 Nanorods: Theoretical and Experimental Investigations

Abstract As a green and sustainable strategy, the electrocatalytic N 2 reduction reaction (NRR) has been considered the best potential approach to replace the traditional Haber‐Bosch process under ambient conditions. The key is to exploit efficient and low‐cost electrocatalysts according to the current situation. Herein, a series of Molybdenum (Mo) doped CeO 2 nanorods (NR) catalysts were successfully fabricated via a hydrothermal reaction coupled with high temperature calcination. The nanorod structures were not altered after Mo atom doping. The obtained 5 %‐Mo‐CeO 2 nanorods act as a superior electrocatalyst in neutral electrolytes of 0.1 M Na 2 SO 4 . Such electrocatalyst significantly enhances NRR performance with an NH 3 yield of 10.9 μg h −1 mg −1 cat at −0.45 V vs reversible hydrogen electrode (RHE) and a Faradaic efficiency (FE) of 26.5 % at −0.25 V vs RHE. That outcome is 4 times higher than that of CeO 2 nanorods (2.6 μg h −1 mg −1 cat ; 4.9 %). Meanwhile, density functional theory (DFT) calculation shows the characteristics after Mo doping: the band gap value lowers, the density of states increases, electrons are more easily excited, and N 2 molecules are more easily adsorbed, thereby enhancing the activity of the electrocatalytic NRR.