Highly Selective N2 Electroreduction to NH3 Using a Boron-Vacancy-Rich Diatomic NbB Catalyst.

The ambient electrochemical N reduction reaction (NRR) is a future approach for the artificial NH synthesis to overcome the problems of high-energy consumption and environmental pollution by Haber-Bosch technology. However, the challenge of N activation on a catalyst surface and the competitive hydrogen evolution reaction make the current NRR unsatisfied. Herein, this work demonstrates that NbB nanoflakes (NFs) exhibit excellent selectivity and durability in NRR, which produces NH with a production rate of 30.5 µg h mg and a super-high Faraday efficiency (FE) of 40.2%. The high-selective NH production is attributed to the large amount of active B vacancies on the surface of NbB NFs. Density functional theory calculations suggest that the multiple atomic adsorption of N on both unsaturated Nb and B atoms results in a significantly stretched N molecule. The weakened NN triple bonds are easier to be broken for a biased NH production. The diatomic catalysis is a future approach for NRR as it shows a special N adsorption mode that can be well engineered.