ZrB2 as an earth-abundant metal diboride catalyst for electroreduction of dinitrogen to ammonia

Abstract

ZrB₂ is first explored as an earth-abundant metal diboride catalyst for highly efficient nitrogen reduction reaction (NRR). The synthesized ZrB₂ nanocubes exhibited a highly attractive NRR performance with an NH₃ yield of 37.7 μg h⁻¹ mg⁻¹ and a Faradaic efficiency 18.2% at −0.3 V (RHE). Theoretical calculations unraveled that active Zr centers enabled the effective activation of the N₂ molecule via a unique tetranuclear side-on mode and concurrently impeded hydrogen evolution by restricting H⁺ adsorption.