Pathway‐Control and Intermediate‐Stabilization in Hydroxylamine Electrosynthesis

ABSTRACT Hydroxylamine (NH 2 OH) is a pivotal industrial intermediate, yet its direct synthesis lacks green and efficient routes. This review addresses the core bottlenecks in electrocatalytic N‐reduction to NH 2 OH: precise control over reaction pathway branching and stabilization of reactive intermediates. We elucidate how the topological configuration of multi‐electron transfer networks dictates selectivity among NH 2 OH, NH 3 , and N 2 , highlighting the decisive role of the *NO intermediate's energy level alignment and surface adsorption geometry. Identifying interfacial charge transfer as a primary kinetic bottleneck, we discuss how modulating the electronic structure of active sites optimizes intermediate adsorption energies. This mechanistic insight is integrated with surface microenvironment engineering strategies to suppress parasitic reactions. We critically assess external fields—including pH gradients, specific electrolyte effects, and nanoconfinement—that enhance mass transfer, stabilize intermediates, and boost local reactant concentrations. To transcend current limitations, we advocate advanced in situ/operando characterization to decode dynamic interfacial processes and multi‐physics coupling. We propose a “three‐stage” dynamic control theory encompassing activation, selective hydrogenation, and product protection. We argue that a green electrosynthesis revolution requires a paradigm shift toward decoupled electrode architectures and holistic system optimization guided by full life‐cycle assessment, positioning this framework as a blueprint for next‐generation catalyst and reactor design.