Electronic Effects of Nitrogen Atoms of Supports on Pt–Ni Rhombic Dodecahedral Nanoframes for Oxygen Reduction

Pt-based nanostructures immobilized on carbon supports have been widely used as electrocatalysts. Their catalytic activity can be improved by support modification including nitrogen doping and coating with nitrogen-containing polymers, where nitrogen atoms possibly interact with surface Pt atoms at a catalyst/support interface. To understand electronic effects of nitrogen-doped and polymer-coated carbon supports on the catalytic activity of Pt-based nanostructured catalysts, we prepared Pt3Ni nanoframes (NFs) supported on polybenzimidazole (PBI)-coated and uncoated carbon nanotubes for the oxygen reduction reaction (ORR), and then compared their catalytic activities and electronic properties with those of NFs immobilized on nitrogen-doped and undoped carbon supports. Although both PBI-coating and nitrogen-doping approaches improved the catalytic activity of NFs, ex situ X-ray photoelectron spectroscopy and in situ X-ray absorption spectroscopy revealed that nitrogen doping showed electronic effects on NFs, whereas PBI-coating showed almost no impact on the electronic state of NFs but stabilized Pt(OH)ad species under electrochemical conditions. Our studies demonstrate that difference in microscopic environments of nitrogen atoms at the catalyst/support interface is highly sensitive to the electronic effects of supports on Pt-based electrocatalysts.