Creation of Highly Dispersed Supported Polyoxometalate Cesium Salts via Cation Exchange from Alkylammonium Salts on Supports

Abstract We have reported several precisely designed metal‐oxo clusters on lacunary polyoxometalate (POM) tetra‐n‐butylammonium (TBA) salts in organic solvents. However, owing to their low thermostability and/or low effective surface area, POM TBA salts are not amenable to heterogeneous catalysts for gas‐phase reactions at high temperature. To avoid this problem, we developed a new preparation method that obtains highly dispersed supported‐POM Cs salts (Cs−POM/support) via cation exchange from the corresponding TBA salts on supports. In this study, a model Keggin‐type POM called TBA₄PVMo₁₁O₄₀ (TBA−PVMo11) is supported on oxides (TBA−PVMo11/support) using an incipient wetness method in acetonitrile. This TBA−PVMo11/support was cation‐exchanged with cesium trifluoromethanesulfonate in ethanol to obtain supported‐POM Cs salts (Cs−PVMo11/support). Various characterizations revealed that the TBA−PVMo11/support maintained the original Keggin structure during cation exchange and that Cs−PVMo11 was highly dispersed on the supports. Furthermore, Cs−PVMo11/support maintained the Keggin structure even after calcination at 573 K under an aerobic condition.