Orchestrating Reactive Intermediates: Unlocking Near-Complete Oxidant Utilization in Electrochemical-Thermal Cascade Oxime Synthesis.

Oxime synthesis via hydroxylamine is the preferred route and is conventionally achieved by ammoxidation of ammonia with hydrogen peroxide. Yet, in alkaline environments, the simultaneous presence of ionic hydroperoxide (OOH-) and molecular H2O2 severely constrains oxidant efficiency. Here, we introduce a life cycle control strategy that coordinates the generation, stabilization, transport, and consumption of OOH- to concentrate it into a centralized OOH- population. Implemented in a continuous electrochemical-thermal cascade operating in weakly protic methanol, this approach enables efficient oxime production directly from ammonia and offers a route to reengineer traditional manufacturing. Detailed mechanistic studies show that the centralized OOH- population yields an oxidant utilization efficiency of up to 96.8% and a 60.3% enhancement in oxime synthesis rate versus conventional thermocatalysis. By establishing a paradigm for regulating the population of a key reactive intermediate, this work delivers guiding principles for the rational design of advanced cascade catalytic systems.