Titanium (Ti) resists corrosion due to spontaneous passivation and subsequent formation of a stable, substantially inert oxide film. This passive film limits the reducing ability of Ti in wet chemical synthesis. Aggressive anions are applied here to destabilize Ti passivity, with the objective of activating Ti as a reducing agent for wet-chemical synthesis, through the formation of unsupported and supported metallic nanoparticles (MNPs). For instance, within the first minute of Ti immersion in a standard gold solution (SGS), 1000 +/- 3 mu g Au/mL in 2% HCl, gold nanoparticles (AuNPs) in solution (unsupported) and a considerable population of highly dispersed AuNPs on Ti (Ti-supported AuNPs) are obtained. This occurs at room temperature, without using reducing agents, stabilizers, or any chemical pre-treatments. Electrochemical measurements revealed that the passivity of Ti was destabilized (oxide thinning/dissolution) in the SGS. The addition of F- to the SGS promoted destabilization of the passive film, and hence activated the reducing ability of Ti. This in turn resulted in significant increase in the population of AuNPs on Ti. Reduction of cations in solution by the active nascent (atomic) hydrogen (H) generated by substrate (Ti) dissolution, promoted by the addition of F-, in acidic medium is confirmed here and discussed vs. conductivity of the oxide (passive) film and solution pH. Experimental findings reveal that the relevance of H as the actual reducing agent is limited to instantaneous and non-conductive passive films. Solution pH studies on such passive films show that the Nernst equation (dE(H/H)(+)/d(pH) = -0.059 V) controls the wet chemical synthesis of MNPs rather than E-reduction(o) of the base metal (the substrate). Based on polarization measurements, the prepared Ti-supported AuNPs are demonstrated here as highly active electrocatalysts (better than Pt) for the hydrogen evolution reaction (HER) in 0.1 M HCl solution. (C) 2014 The Electrochemical Society. All rights reserved.