Vapor-phase selective hydrogenation of crotonaldehyde was conducted over Ir/SiO2 catalysts to investigate the effects of Ir loading on the catalytic behaviors. The catalysts were characterized by X-ray powder diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), CO chemisorption, temperature-programmed reduction (TPR), diffuse reflectance infrared Fourier transform spectra of CO adsorption (CO-DRIFTS), NH3 temperature-programmed desorption (NH3-TPD), and temperature-programmed oxidation (TPO). It was found that the particle size of Ir in the catalyst increased with Ir loading, being 2.1, 3.9 and 6.7 nm for the 1Ir/SiO2, 3Ir/SiO2 and 5Ir/SiO2 catalyst, respectively. The Ir species on the Ir/SiO2 catalysts consisted of Ir-0 and Ir delta+, but the average valence of Ir species decreased with increasing Ir loading. Also, catalytic testing results revealed that the reactivity of the catalyst increased with Ir loading. Interestingly, it was found that the reaction underwent an induction period, with the conversion of crotonaldehyede and the selectivity to crotyl alcohol gradually increasing during the reaction, and eventually reaching a steady state. The highest selectivity (77.6%) to crotyl alcohol was obtained over the 3Ir/SiO2 catalyst, and the conversion increased gradually to 15.6%. The catalytic behavior of these stable catalysts could be attributed to the proper Ir particle size, the existence of Ir-0 and Ir delta+ species on the surface, and high amount of surface acid sites in these catalysts. (c) 2013 Elsevier B.V. All rights reserved.