Benzyl alcohol to benzaldehyde oxidation on MnOx clusters: Unraveling atomistic features

•Catalytic oxidation of benzyl alcohol to benzaldehyde over MnOx catalysts is analyzed in the DFT framework.•Oxidation reactivity and selectivity over cluster-sized Mn4O8 and Mn4O9 catalytic models is compared.•Catalyst poisoning is addressed by investigating the formation of benzoic acid following that of benzaldehyde.•Reaction steps and the related oxidation pathways are collected and analyzed by an original kinetic approach.•Experimental strategies aimed at decreasing catalyst deactivation hence at increasing selectivity are proposed.