Benzene hydrogenation was investigated in the presence of a surface monolayer consisting of Pt nanoparticles of different shapes (cubic and cuboctahedral) and tetradecyltrimethylammonium bromide (TTAB). Infrared spectroscopy indicated that TTAB binds to the Pt surface through a weak C-HâââPt bond of the alkyl chain. The catalytic selectivity was found to be strongly affected by the nanoparticle shape. Both cyclohexane and cyclohexene product molecules were formed on cuboctahedral nanoparticles, whereas only cyclohexane was produced on cubic nanoparticles. These results are the same as the product selectivities obtained on Pt(111) and Pt(100) single crystals in earlier studies. The apparent activation energy for cyclohexane production on cubic nanoparticles is 10.9 ± 0.4 kcal/mol, while for cuboctahedral nanoparticles, the apparent activation energies for cyclohexane and cyclohexene production are 8.3 ± 0.2 and 12.2 ± 0.4 kcal/mol, respectively. These activation energies are lower, and corresponding turnover rates are three times higher than those obtained with single-crystal Pt surfaces.