An emerging method for effectively improving the catalytic activity of metal oxide hybrids involves the creation of metal oxide interfaces for facilitating the activation of reagents. Here, we demonstrate that bilayer vesicles formed from a hexavanadate cluster functionalized with two alkyl chains are highly efficient catalysts for the oxidation of 3, 3′, 5, 5′-tetramethylbenzidine (TMB) with H₂O₂ at room temperature, a widely used model reaction mimicking the activity of peroxidase in biological catalytic oxidation processes. Driven by hydrophobic interactions, the double-tailed hexavanadate-headed amphiphiles can self-assemble into bilayer vesicles and create hydrophobic domains that segregate the TMB chromogenic substrate. The reaction of TMB with H₂O₂ takes place at the interface of the hydrophilic and hydrophobic domains, where the reagents also make contact with the catalytic hexavanadate clusters, and it is approximately two times more efficient compared with the reactions carried out with the corresponding unassembled systems. Moreover, the assembled vesicular system possesses affinity for TMB comparable to that of reported noble metal mimic nanomaterials, as well as a higher maximum reaction rate.

Two-dimensional nanomaterials have become a hot research topic, and progress in research on them in the past decade has been substantial. Here we demonstrate a molecule-based bottom-up method to synthesize freestanding polyoxometalatebased nanosheets in two different ways. The trans substitution of ligands with carboxylate functionality promoted the coordination of organically derivatized hexavanadate with zinc ions with preferential directionality, which led to the formation of coordination polymer nanosheets. Characterization with transmission electron microscopy, powder X-ray diffraction, and infrared spectroscopy confirmed the morphology, structural composition, and preferential direction of the nanosheets. The microwave-assisted heating method and solvent addition method were proved to be effective for the preparation of POM-based nanosheet structures. The nanosheets were found to catalyze the aerobic oxidation of propanethiol (n-PrSH) to its corresponding disulfide (PrSSPr) under mild conditions.