Licht et al. (Science, 2014, 345, 637) recently proposed a procedure to synthesize NH3 from N2 and by steam electrolysis in molten hydroxide suspensions of nano-Fe2O3. This highly exciting investigation undoubtedly boosts the hope of the CO2-free and low-cost ammonia industry. To provide insights at the atomistic level into the reduction process of N2, we have carried out a density-functional study on the electrochemical formation of NH3 molecules on hematite(0001) surfaces. By considering associative and dissociative mechanisms, we have identified a reaction path that requires an applied bias of -1.1 V to allow the proton transfer processes to occur downhill. The most energy-demanding step is the addition of the first proton to the adsorbed molecular nitrogen. The computed bias is in good agreement with experimental electrolysis potentials that activate the electric current.