By combining theoretical modelling, in situ spectroscopy and kinetic studies it is possible to understand, at the molecular level, the role that the different types of active centres co-existing on real heterogeneous catalysts play on each elementary step of the global reaction mechanism. The fundamental knowledge acquired by means of this multi-disciplinary approach in two selected reactions, the chemoselective hydrogenation of substituted nitroaromatics and the Sonogashira coupling between aryl halides and alkynes, is applied to direct the rational synthesis of more efficient industrial catalysts based on noble metal particles supported on metal oxides. (C) 2016 Elsevier B.V. All rights reserved.