Selective electrooxidation of 2-propanol on Pt nanoparticles supported on Co 3 O 4 : an in-situ study on atomically defined model systems

2-Propanol and its dehydrogenated counterpart acetone can be used as a rechargeable electrofuel. The concept involves selective oxidation of 2-propanol to acetone in a fuel cell coupled with reverse catalytic hydrogenation of acetone to 2-propanol in a closed cycle. We studied electrocatalytic oxidation of 2-propanol on complex model Pt/Co 3 O 4 (111) electrocatalysts prepared in ultra-high vacuum and characterized by scanning tunneling microscopy. The electrocatalytic behavior of the model electrocatalysts has been investigated in alkaline media (pH 10, phosphate buffer) by means of electrochemical infrared reflection absorption spectroscopy and ex-situ emersion synchrotron radiation photoelectron spectroscopy as a function of Pt particle size and compared with the electrocatalytic behavior of Pt(111) and pristine Co 3 O 4 (111) electrodes under similar conditions. We found that the Co 3 O 4 (111) film is inactive towards electrochemical oxidation of 2-propanol under the electrochemical conditions (0.3–1.1 V RHE ). The electrochemical oxidation of 2-propanol readily occurs on Pt(111) yielding acetone at an onset potential of 0.4 V RHE . The reaction pathway does not involve CO but yields strongly adsorbed acetone species leading to a partial poisoning of the surface sites. On model Pt/Co 3 O 4 (111) electrocatalysts, we observed distinct metal support interactions and particle size effects associated with the charge transfer at the metal/oxide interface. We found that ultra-small Pt particles (around 1 nm and below) consist of partially oxidized Pt δ + species which show minor activity towards 2-propanol oxidation. In contrast, conventional Pt particles (particle size of a few nm) are mainly metallic and show high activity toward 2-propanol oxidation.