Global
ammonia production reached 175 million metric tons in 2016,
90% of which is produced from high purity N2 and H2 gases at high temperatures and pressures via the Haber–Bosch
process. Reliance on natural gas for H2 production results
in large energy consumption and CO2 emissions. Concerns
of human-induced climate change are spurring an international scientific
effort to explore new approaches to ammonia production and reduce
its carbon footprint. Electrocatalytic N2 reduction to
ammonia is an attractive alternative that can potentially enable ammonia
synthesis under milder conditions in small-scale, distributed, and
on-site electrolysis cells powered by renewable electricity generated
from solar or wind sources. This review provides a comprehensive account
of theoretical and experimental studies on electrochemical nitrogen
fixation with a focus on the low selectivity for reduction of N2 to ammonia versus protons to H2. A detailed introduction
to ammonia detection methods and the execution of control experiments
is given as they are crucial to the accurate reporting of experimental
findings. The main part of this review focuses on theoretical and
experimental progress that has been achieved under a range of conditions.
Finally, comments on current challenges and potential opportunities
in this field are provided.