An easily accessible Re-based catalyst for the selective conversion of methanol: evidence for an unprecedented active site structure through combined operandotechniquesElectronic supplementary information (ESI) available: Characterization of the pure SiO2support; compared TPR profile of 10ReSiand 10%ReOx/Aerosil 200; procedure for catalytic test; EXAFS procedure. See DOI: 10.1039/c0cc05542e

Heterogeneous Re/SiO2catalysts prepared using a one pot sol–gel synthesis were found to display high activity in the direct, selective methanol conversion to methylal, which is correlated to an unprecedented rhenium oxide structure. [ABSTRACT FROM AUTHOR]