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To investigate the influence of particle size in terms of electrocatalysis for the hydrogen evolution reaction (HER), small Pt  n   species withn  =   1  ,  10  ,  13$n=1,10,13$    atoms and nanoparticles are deposited onto native titanium dioxide. These species are compared to the bare support as well as to bulk platinum with respect to the catalytic activity. Photoelectron spectroscopy showed Pt4f core-level shifts to higher binding energies with decreasing cluster size. In addition, the various species contribute significant density of states into the valence band gap of TiO 2 , thereby with larger particle size, the resulting band gap narrows. For nanoparticles, metal-like behaviour was already observed. Electrochemical measurements in 0.1 M H 2 SO 4  showed the highest overall catalytic activity for bulk platinum and large Pt nanoparticles. A different assertion is obtained when the activities are related to the mass of the catalyst used, indicating that clusters with a size of about ten atoms seem to be most active. In comparison with the results from photoelectron spectroscopy regarding the electronic structure, no clear correlation to the catalytic activity was found. In terms of degradation induced due to the electrochemical treatment, the cluster samples showed no sintering effects, but instead, some detachment took place.

From Bulk to Atoms: The Influence of Particle and Cluster Size on the Hydrogen Evolution Reaction