The ammoximation of ketones to the corresponding oxime via the in situ production of H 2 O 2 offers a viable alternative to the current means of industrial-scale production, in particular for the synthesis of cyclohexanone oxime, a key precursor to Nylon-6. Herein, we demonstrate that using a bifunctional catalyst, consisting of Pd-based bimetallic nanoparticles immobilized onto a TS-1 carrier, it is possible to bridge the considerable condition gap that exists between the two key distinct reaction pathways that constitute an in-situ approach (i.e., the direct synthesis of H 2 O 2 and ketone ammoximation). The formation of PdAu nanoalloys is found to be crucial in achieving high reactivity and in promoting catalytic stability, with the optimal formulation significantly outperforming both alternative Pd-based materials and the monometallic Pd analogue.

The introduction of dopant concentrations of Pt into supported AuPd nanoparticles, when used in conjunction with an evolved unspecific peroxygenase (UPO) from Agrocybe aegerita (PaDa-I) is demonstrated to offer high efficacy towards the one-pot selective oxidation of cyclohexane to KA oil (cyclohexanol and cyclohexanone), via the in-situ synthesis of H 2 O 2 . The optimised AuPdPt/TiO 2 /PaDa-I system achieves significant improvements over analogous AuPd or Pd-only formulations or the use of commercially available H 2 O 2 , with this attributed to the increased rate of H 2 O 2 production by the chemo-catalyst, which results from the electronic modification of Pd species via Pt incorporation, upon the formation of trimetallic nanoalloys.

Schematic of the proposed structure for a high Al doped haematite sample with MoOx overlayers.