First-Principles Insights into the Thermodynamics of Variable-Temperature Ammonia Synthesis on Transition-Metal-Doped Cu (100) and (111)

Ammonia (NH 3 ) is one of the most produced chemicals worldwide. NH 3 synthesis predominantly utilizes the Haber–Bosch (HB) process, requiring high temperatures and pressures. Despite significant process advances, ample opportunity remains for improving the rate, selectivity, catalyst stability, and energy efficiency. Inspired by a recently developed programmable heating and quenching (PHQ) technique, here we present a first-principles screening of candidate single-atom alloy catalysts generated from doping (111) and (100) surfaces of copper (Cu), an ineffective HB catalyst in its pure form. We predict the thermodynamics of two rate-limiting reactions, N 2 dissociative adsorption and the final hydrogenation step leading up to NH 3 release, at 400 and 900 K. Thermodynamically, the former reaction is favored at low temperatures, while the latter is favored at high temperatures. Vanadium-, chromium-, and molybdenum-doped Cu surfaces, due to intermediate M–N covalent bonding character, emerge as appealing candidate catalysts for PHQ NH 3 synthesis, as they balance the thermodynamics of the above-mentioned reaction steps at their respective optimal temperatures.