The activation of dihydrogen on silica, silver, and silica-supported silver (9 wt% Ag) was investigated. Both silica and silver are individually able to dissociate dihydrogen. Silanol groups on silica undergo H -> D exchange at 393 K in D-2 as detected by IR spectroscopy. HD is observed in temporal analysis of products (TAP) experiments when H-2 and D-2 are sequentially pulsed on silver at 673 K; even when the time delay between the isotopes is 4 s, HD is formed, indicating that long-lived surface hydrogen species are present. Differential scanning calorimetry (DSC) shows that the activation of dihydrogen is an activated process: heat signals evoked through H-2 Pulses on Ag/SiO2 grow with increasing temperature (373-523 K). Nonetheless, the presence of silver on the silica surface accelerates the Si-OH -> Si-OD exchange. Investigation of the exchange kinetics on Ag/SiO2. shows that diffusion processes of the activated hydrogen species are rate determining at higher temperatures (>= 373 K), when the activation of D-2 on silver becomes facile. Indications of diffusion limitation are observed already at 313 K on Pt/SiO2. TAP and DSC measurements show that H-2 is More readily activated on silver that has been treated in O-2 at 673 K followed by reduction in H-2 at 673 K. Morphological changes induced to the silver surfaces or (sub)surface oxygen species are presumed responsible for this effect. (c) 2009 Elsevier Inc. All rights reserved.