The ammoximation of cyclohexanone using preformed hydrogen peroxide (H ₂ O ₂ ) is currently applied commercially to produce cyclohexanone oxime, an important feedstock in nylon-6 production. We demonstrate that by using supported gold-palladium (AuPd) alloyed nanoparticles in conjunction with a titanium silicate-1 (TS-1) catalyst, H ₂ O ₂ can be generated in situ as needed, producing cyclohexanone oxime with >95% selectivity, comparable to the current industrial route. The ammoximation of several additional simple ketones is also demonstrated. Our approach eliminates the need to transport and store highly concentrated, stabilized H ₂ O ₂ , potentially achieving substantial environmental and economic savings. This approach could form the basis of an alternative route to numerous chemical transformations that are currently dependent on a combination of preformed H ₂ O ₂ and TS-1, while allowing for considerable process intensification.

Bimetallic Pd-Fe catalysts supported on TiO₂ are shown to be highly effective toward the selective oxidation of benzyl alcohol to benzaldehyde via the in situ production of H₂O₂ from molecular H₂ and O₂, under conditions where no reaction is observed with molecular O₂ alone. The rate of benzyl alcohol oxidation observed over supported Pd-Fe nanoparticles is significantly higher than those of either Pd-Au or Pd-only analogues. This enhanced activity can be attributed to the bifunctionality of the Pd-Fe catalyst to both synthesize H₂O₂ and catalyze the production of oxygen-based radical specie,s as indicated by an electron paramagnetic resonance analysis. Further studies also reveal the noninnocent nature of the solvent, resulting in the propagation of radical generation pathways.