Bimetallic AuAg/SBA-15 catalysts were disclosed to efficiently catalyze vapor-phase chemoselective hydrogenation of crotonaldehyde (CRAL) with improved hydrogenation rate and selectivity to crotonyl alcohol (CROL). The CRAL hydrogenation rate and product distribution were remarkably influenced by reaction parameters such as the reaction pressure and CRAL/hydrogen ratio. Ag decoration on Au/SBA-15 effectively stabilized bimetallic AuAg nano-alloy particles in small size and promoted the catalytic stability. In situ FT-IR investigation revealed that unusual C2M2 di-sigma bonded CRAL surface species with reinforced symmetric delta(CH3) IR band under the "metal-surface selection rule" (MSSR) were formed on bimetallic AuAg/SBA-15. The stronger CRAL chemisorption on bimetallic AuAg/SBA-15 surfaces than on monometallic Au/SBA-15 was possibly due to the relatively strong ligating of C=O bond on Ag active sites and the enhancement of the co-adsorption of the conjugated double bonds of CRAL. Synergistic interaction between Au and Ag active sites for the activation of H-H, C=C and C=O bond may be the origin of positive effect of Ag decoration on Au/SBA-15. (C) 2015 Elsevier Inc. All rights reserved.