Oxygen Vacancies of CeO₂ Nanospheres by Mn-Doping: An Efficient Electrocatalyst for N₂ Reduction under Ambient...

The electrochemical N₂ reduction reaction (NRR) demonstrates a process of NH₃ synthesis from N₂ molecules under ambient conditions, which is environmentally friendly and recyclable. However, it requires an efficient electrocatalyst to activate inert N₂ molecules, which is still difficult to satisfy. Recently, as an active NRR electrocatalyst and a typical metal oxide, CeO₂ has featured ultrahigh thermal stability and the ability to apply heteroatom doping, which is an imperative approach importing oxygen vacancy by replacing metal ions with selective elements to greatly influence the activity of catalysts. Here, we analyze the unique properties of manganese dopants in modulating the activity of CeO₂ nanospheres for NRR. It attains a larger NH₃ yield of 27.79 μg h^-1 mg_cat^-1 and a higher Faradaic efficiency of 9.1% than pure CeO₂ at -0.30 V in 0.1 M HCl, with high electrochemical and structure stability. With calculations by density functional theory, the performance enhancement of Mn-doped CeO₂ is also proved mathematically.