Synergistic Oxidation of Mustard Simulants by Vanadium‐Substituted Polyoxomolybdate Ionic Crystals Assembled With an Aluminum Oxo‐Hydroxide Cluster

Two porous ionic crystals (PICs), δ‐Al13‐PMo10V2 and δ‐Al13‐PMo9V3, were synthesized by assembling vanadium‐substituted Keggin‐type polyoxomolybdates with the oxidatively robust aluminum oxo‐hydroxide cation (δ‐Al13). Single‐crystal X‐ray diffraction analysis revealed that the two PICs are isostructural, forming one‐dimensional channels, while δ‐Al13‐PMo10V2 possesses a larger pore volume. Both PICs act as efficient solid catalysts for the selective oxidation of mustard simulant 2‐chloroethyl ethyl sulfide (CEES) with H2O2 under mild conditions, and δ‐Al13‐PMo10V2 achieved nearly complete conversion and selectivity within 36 min. The higher activity of δ‐Al13‐PMo10V2 can be attributed to its more favorable redox characteristics and enhanced mass transport. The δ‐Al13 cluster not only stabilizes the solid‐state structure but also modulates the electronic environment, resulting in synergistically enhanced oxidation catalysis.