Catalytic hydrogenolysis of glycerol to value-added 1,3-propanediol (1,3-PDO) holds the potential to utilize the large surplus of crude glycerol from biodiesel industry. A series of alkaline metals (Li, K, Rb and Cs) modified Pt-H4SiW12O40/ZrO2 catalysts were prepared, characterized and evaluated for this reaction. The bulk and surface features of these catalysts were characterized by several techniques, including BET, CO-chemisorption, XRD, Raman, SEM-EDX, NH3-TPD and FTIR of adsorbed pyridine. Among them, Li exchanged H4SiW12O40 (HSiW) exhibited superior activity and maximum 1,3-PDO selectivity due to the enhanced Bronsted acid sites. This catalyst achieved 120h long-term stability owing to the strong interaction of active components with ZrO2, remaining of unique Keggin structure as well as the enhanced water-tolerance. There is a linear relationship between 1,3-PDO yield and concentration of Bronsted acid sites, providing direct evidence that Bronsted acid sites are responsible for the selective formation of 1,3-PDO from glycerol hydrogenolysis. (C) 2013 Elsevier B.V. All rights reserved.