Vacancy-enhanced Mo-N2 interaction in MoSe2 nanosheets enables efficient electrocatalytic NH3 synthesis

NH3 plays an essential role in human life since it is an important raw material for fertilizers, plastics and rubbers production. As an NH3 synthesis technology under ambient conditions, electrocatalytic N2 reduction reaction (NRR) has great potential to replace the energy-intensive Haber-Bosch process. The key of electrocatalytic NRR is the exploration of efficient catalysts. Transition metal Mo is promising since it exists naturally in nitrogenase due to the unique Mo-N2 interaction; particularly in the form of 2D material such as MoSe2, the surface area is maximized for more active sites. However, the NRR performance of MoSe2 is still unsatisfactory because Mo is only exposed at the semi-open edge, and the electronegative Se-mantled surface area remains inaccessible to N2. Herein, we propose a simple and effective strategy to create high-concentration Se vacancies in MoSe2 through heteroatom doping induced lattice strain, which effectively enhances the Mo-N2 interaction on the surface area. In result, high NH3 yield (3.04 × 10–10 mol s–1 cm–2) and Faraday efficiency (21.61%) are attained at –0.45 V vs. RHE in 0.1 mol/L Na2SO4.