The combination in one catalytic system of the aqueous phase reforming (APR) reaction of small alcohols to generate in-situ the H2 necessary to the hydrogenolysis (APH) of glycerol is a promising process to produce 1,2- and 1,3-propanediols, which are fundamental for the sustainable manufacture of plastics, drugs, etc. We investigated this process using a series Ni-Cu bimetallic catalysts supported on Mg-Al oxides. The results indicate that the combination of the two metals is vitalto achieve high propanediol selectivity but do not ensure stability. While some insights on this latter issue are available, to date, the precise role of the two metals as well as that of the Mg support in performing APR and APH in a single catalytic system are not clear. Scope of this proposal is to unravel the evolution of the catalytic system under operando conditions, in order to provide a rational on the exceptionally high selectivity of Cu-Ni catalysts while understanding the deactivation mechanism.