Descriptor‐Based Volcano Relations Predict Single Atoms for Hydroxylamine Electrosynthesis

Abstract Hydroxylamine (NH 2 OH) is an important feedstock in fuels, pharmaceuticals, and agrochemicals. Nanostructured electrocatalysts drive green electrosynthesis of hydroxylamine from nitrogen oxide species in water. However, current electrocatalysts still suffer from low selectivity and manpower‐consuming trial‐and‐error modes, leaving unclear selectivity/activity origins and a lack of catalyst design principles. Herein, we theoretically analyze key determinants of selectivity/activity and propose the adsorption energy of NHO ( G ad (*NHO)) as a performance descriptor. A weak *NH 2 OH binding affinity and a favorable reaction pathway (*NHO pathway) jointly enable single‐atom catalysts (SACs) with superior NH 2 OH selectivity. Then, an activity volcano plot of G ad (*NHO) is established to predict a series of SACs and discover Mn SACs as optimal electrocatalysts that exhibit pH‐dependent activity. These theoretical prediction results are also confirmed by experimental results, rationalizing our G ad (*NHO) descriptor. Furthermore, Mn−Co geminal‐atom catalysts (GACs) are predicted to optimize G ad (*NHO) and are experimentally proved to enhance NH 2 OH formation.